Spiroheterocyclic Photocatalyst for Reducing QHIn-Persistent Pollutants, Dyes, and Transition-Metal Ions Cocatalyzed with Electrolytes

The 7-nitro-2′-phenyl-5′,6′,7′,7a′-tetrahydrospiro[indeno[1,2-b]quinoxaline-11,3′-pyrrolizine]-1′,1′(2′H)-dicarbonitrile (SIQPI), 2′-(4-cyanophenyl)-7-nitro-5′,6′,7′,7a′-tetrahydrospiro[indeno[1,2-b]quinoxaline-11,3′-pyrrolizine]-1′,1′(2′H) dicarbonitrile (SIQPII), and 2′-(4-methoxyphenyl)-7-nitro-5′,6′,7′,7a′-tetrahydrospiro[indeno[1,2-b]quinoxaline-11,3′-pyrrolizine]-1′,1′(2′H)-dicarbonitrile (SIQPIII) were used to photocatalyze quinonoid phenolphthalein (QHIn) in aq-ACN-EtOH (mixed solvent) with NaCl and KCl electrolytes. SIQPI, II, and III spiroindenoquinoxaline pyrrolidines (SIQPs) as spiroheterocyclic photocatalysts alone could not reduce QHIn, but with the addition of electrolytes they are reduced via π cationic interactions (PCI). SIQPI, II, and III with NaCl reduced QHIn in 120, 28, and 50 min, unlike in 138, 58, and 63 min with KCl in mixed solvent. SIQPI, II, and III alone have reduced methylene blue (MB) in 120, 45, and 70 min, unlike in 110, 27, and 55 min with graphene oxide (GO), whereas with NaCl and KCl hey are reduced in 82, 36, and 44 min and 89, 43, and 50 min, respectively. SIQPs with GO had reduced MB in less time than the SIQPs alone, and SIQPs with NaCl had reduced QHIn in a shorter time than KCl. The electrolytes have cocatalyzed a reduction of dyes under sunlight (SL). The electrolytes have reduced a quinonoid structure (QS) and dyes by generating negative and positive (e– and h+) holes in a shorter time. SIQPII and magnetic nanoparticles (MNPs) of 58 nm with NaCl photocatalyzed the QHIn in 2880 min. The SIQPs also reduced methyl orange (MO) and brilliant blue R (BBR) at variable temperature (T) and pH range, whereas SIQPs have developed a molecular organic framework (MOF) with transition-metal salts (NiCl2, CrO3, KMnO4, CuSO4, and MnCl2) on photocatalysis.


INTRODUCTION
SIQPs with a higher polarizability have negligible conductivity (4 × 10 −6 S cm −1 ) (Figures 1 and S1(a−c)). The SIQPs and GO both have photocatalytically reduced (PCR) the MB 1 individually and together. These experiments have inspired us to reduce QHIn, BBR, MO, and transitional-metal ions by SIQPs. SIQPs alone have reduced BBR and MO at pH 4 and 8 and formed a MOF with the transition metals but could not reduce the QHIn at pH 8 in the absence of electrolytes under SL. Phenolphthalein (HIn) with aq-NaOH is transformed into QHIn having an electronically stable QS. Thus, the QS having high potential inhibited the electronic oscillations or excitation to a higher energy state as a harmonized wave function (ψs). The electronic harmonization is weakened by electrolytes via developing PCI with the QHIn using short sized Na + unlike Ba 2+ (BaCl 2 ) for reduction at constant pH and split of water. Also, the electrolytes have cocatalyzed the SIQPs to enhance an intensity of ψ of the e − and h + holes where the e − and h + holes have counterbalanced the respective holes of the reducing species by minimizing their quantum energy barrier (QEB) with a high quantum yield (Φ). The ions of the electrolytes could have aligned the electrostatic sites of the SIQPs with QHIn via enhancing redox cycles (ROC). This route to SIQPs− electrolyte interfaces could lead to a greener 2 PCR mechanism for QHIn, a persistent pollutant by SIQPs at constant pH. Also, SIQPs with MNPs could not reduce the QHIn but were reduced with electrolyte in 48 h. The MNPs seem to align the QHIn with stronger adhesive forces and have generated high QEB and permittivity (ε), and the holes fail to overcome these barriers. The PCR of dyes was analyzed with UV−vis and fluorescence spectroscopy via photochemical and quantum activities of SIQPs, which have not been reported yet (Table S1). Transitional metallic sulfide 3 nanoparticles (NPs) doped with GO have enhanced MB reduction by 18.29%. Similarly, they have resonated the energy of SIQPs to reduce QHIn. The resonating QS transferred their energy to PCR and polarizability supported dipole−dipole resonance energy transfer (DRET) via Forster resonance energy transfer 4 (FRET); e.g., SIQPII with 2CN and CN via chiral a carbon atom (CCA) could have aligned the dipoles to PCR dyes. The Na + and Cl − align a solvent to reorient and respond to e − and h + holes. The zetapotential (ζ) of SIQPs develop a DRET with electron-releasing (ERG) and electron-withdrawing functional groups (EWG). The electrolytes seem to transform a potential energy (PE) to kinetic energy (KE) to photocatalyze the QHIn via disrupting QS and aligning SIQPs for higher polarizability. The CCA induces a polarizability by aligning electronic sites of the SIQPs to reduce dyes. The SIQPs with electrolytes increase a mean free path (MFP) of holes enhanced by minimizing QEB to drastically reduce 5 the QHIn. The electrolytes promote harmonic oscillations to enhance polarizability of SIQPs 6,7 to PCR the QHIn. Despite large advancements in photocatalysts, their simulation with electrolyte was never explored. Also, the electrolytes have mutually solubilized a diphasic medium to monodisperse the SIQPs for a quick photon (hν) response to PCR a dye as there is no single solvent that can homogenize both the photocatalyst and cocatalyst. The different electronic configurations of SIQPs align with the electrolytes to disrupt QS for PCR. The persistent pollutants harm a whole environment but no photocatalysts are there to dissolve and photodegrade them. The SIQPs in mixed solvent with electrolytes on widening the solubilizing activities have reduced QHIn contrary to MNPs 8 (Table 1).

RESULTS AND DISCUSSION
CCA connects nitroindenoquinoxaline-11-one (NIQ) (ψ NIQ ), the phenyl ring, and pyrrolizidine (pyz) (ψ pyz ) of the SIQPs template as ψ NIQ > CCA < ψ pyz that selectively responds to hν ( Figure 1). The CCA aligns oscillations of SIQPs with certain ψ in a symmetric wavevector enhancing the electronic probability 1 |ψ| 2 . Free phenyl (FP) of SIQPI aligns the e − and h + holes whereas the NC-phenyl of II and H 3 CO-phenyl with III reorient the electronic clouds via spatial ψ NIQ and ψ pyz notches. The SIQPs reduced MB in aq-ACN 1 and extended to photocatalyze the QHIn, BBR, MO, and transtion-metal ions in the presence of electrolytes in mixed solvent. The SIQPs alone failed to PCR the QHIn due to its QS with a higher QEB. The QS disruption has been challenged due to highly aligned electronic configurations with a minimum energy of 53.87 kcal/mol and dipole−dipole of 5.12 D than HIn with 22.89 kcal/mol and 8.29 D inhibiting the H bonding. The QS restricts HOMO → LUMO via π → π* with symmetric ψ to maintain an electronically equilibrated structure with no stretching frequency difference (Δν = 0). The Δν = 0 state could not generate a spontaneity with QHIn unlike other dyes with electron-deficient sites to attract the e − and h + holes. Therefore, the Na + and Cl − interact with QHIn as the electrons of its double bonds develop electronic spins with a higher oscillating energy to intensify the ψ with a large number of e − and h + holes. The ψ SIQPs with dipole resonance connects the ψ QHIn mutually via DRET.
2.1. DLS Analysis. The holes align and generate the polarizability, PDI, ζ, surface charges, and particle% passage (Figures 2 and S2). Fractional positive and negative charges of NIQ and pyz respond to hv to align the charges and develop the ζ with higher photocatalytic activities. The linkages of a solvent align the e − and h + holes around CCA by averting intermixing of ψ electronic clouds of pyz and NIQ individually to avoid their recombination. The CCA avoids collisions of holes for a longer MFP to contact the ψ QHIn . The electronically rich and deficient holes oscillate with ψ − and ψ + to interact with the respective sites of QHIn and the other dyes to hybridize with |ψ| 2 . The ψ solvent with a moderately reversible interaction get activated to align with active charges of the dyes. The sharp distribution of SIQPI infers fewer interacting sites with solvent than SIQPII and III. The NC-phenyl EWG and H 3 CO-phenyl ERG (e − and h + ) disrupt a delocalization to generate another center with certain hole density. SIQPII and III are not sharply distributed size wise and generate different ζ compared to I due to FP (Figure 2). SIQPs realign holes with a higher ζ to enhance a photocatalytic reduction of QHIn as their electronic sites oscillate with certain ψ. The ψ of the e − and h + holes of SIQPs interact with ψ solvent e − and ψ solvent h + to align with prominent charges of dyes.
2.2. XRD Analysis. NIQ, pyz, and FP lattices around CCA have generated electronic intensities contrary to CN/EWG that did not develop independent peaks except for CCA ( Figure 3). The SIQPII filters ψ compared to I with delocalized electron cloud center in continuity of CCA. The SIQPI having FP and connected to pyz via CCA and NIQ with different π conjugated systems split sharply. The intensified delocalized FP with multiple sharper peaks is unable to conjugate with other units. NIQ peaks with different intensities and vibrations due to a residual e − charge along the lattices, differing from SIQPI by FP so the CCA mildly tunes the FP, NIQ, and pyz. The SIQPI attains a crystalline structure with α (NIQ) and β (phenyl and pyz) templates. NIQ, pyz, and FP, the negatively charged delocalized centers, sharpened the peaks at the >2θ value ( Figure 3). Their electronic clouds with dipole−dipole interaction (DDI) transfer mutually around the CCA. The CCA equilibrates their surface charges with different electronic clouds to influence the electronic scintillations. XRD 9 has predicted the overall charges, size, and lattice alignments at certain d spacing vis-a-vis inner orbital electrons; e.g., FP of SIQPI induces a milder photocatalytic activity with a weaker coordination among the pyz and NIQ. These may not minimize a QEB unlike the II and III with EWG and ERG, respectively. Had there been a closely packed template structure then there would have not been a chance to respond to the hv similar to the QS. Their symmetric oscillations configure a single sharper XRD infers a disruption of SIQPI compared to NIQ alone within 2θ ∼ 10−35°despite its crystallinity. The NC-phenyl and 2NCpyz units affect the electronic activities of CCA via an interconnecting C atom in response to its 1s electron. The NC-phenyl defused intensities have induced an electronic continuity via CCA ( Figure 3). The CN and OCH 3 have developed a mild sharpness of oscillations and are unable to determine a d spacing, respectively ( Table 2). The CN has shortened the d spacings with the least split so a Raman-inactive 1 and FT-IR-active SIQPII has lowered its polarizability, resulting an infinite stretching. The electrolytes induced the electronic oscillations in QHIn. The higher Raman 1 intensities of SIQPII than I and III as 2LPE of OCH 3 delocalized with phenyl of III manifolding the EER by weakening a polarizability. The higher continuity in XRD peaks of SIQPII than III and I is due to a slightly high activity of EWG. The NIQ alone has delocalized the  electronic activities with the sharper intensities at 2θ = 25°, 2000 au compared to SIQPs ( Figure 3). The weakening of XRD intensities by ∼88% from NIQ to SIQPs with FP, CN, and OCH 3 stabilize their respective oscillations. The EWG and ERG have enhanced Φ of the dyes by minimizing a QEB, 16 and NIQ via CCA supports a framework of SIQP dipolar stability for generating the holes. SIQPIII with OCH 3 compared to II has enhanced a sharper intensity due to 3σ bonds and 2LPE of the O atom with a higher stability and a lowest weight (wt) loss. The SIQPs having multiple sharper peaks alignments could not produce a single lattice as the contributory units induce distinctive scintillations by aligning their charges. The SIQPs compared to NIQ (∼2000 au) alone have stabilized their scintillating intensity as CCA has equilibrated the SIQPs ( Figure  3). NIQ shows a higher melting point than SIQPs with a least wt loss 1 as the different functional sites via FRET equilibrated their energies. The NIQ shaper peaks infer a charge stabilization ( Figure 3).

AFM Analysis.
Functional sites are vibrantly reoriented in space with an integrated topography ( Figure S3(a−c)). SIQPI topography is symmetric along a z-axis distribution forming upward ridges with an almost equal population ( Figure  S3(a)). The CCA of SIQPI could have aligned the NIQ, pyz, and FP with certain residual charges responding to AFM which could have localized the electron clouds and could not homogenize a topography ( Figure S3(a)). Their oscillations occur with upward growth to analyze their oscillations independently or coordinatedly ( Figure S3(a)). Thus, a surface profile interconnects a polarization of charges explained with Raman spectroscopy. 1 The independent FP, NIQ, and 2NC-pyz have responded to a laser to generate the e − and h + holes for PCR. The CCA could not integrate a topography as electronic cloud of each constituent is detained. The SIQPI topography acted as an active recipient for hv and Na + and Cl − that catalyze its functional sites acting as a cocatalyst. Hence, the e − and h + holes and ionic species jointly reduced a QHIn. The electronic clouds of NIQ, pyz, and NC-phenyl units interfaced with the NaCl ions to weaken the QS to PCR QHIn. The NC-phenyl had caused a topographical outward growth along the z-axis to reorient a whole topography due to NO 2 and 2NC-pyz ( Figure  S3(b)). NC-phenyl interacted with the Na + and Cl − charges and also aligned the QHIn, illustrated by Raman and TGA reported previously. 1 The FP reoriented the SIQPI but the II aligns linearly due to NC-phenyl depicted by TGA curve. Had there been completely integrated peaks with SIQPII then the z outward growth could have not existed. NIQ, pyz, and NCphenyl constituents had generated the electrostatic topography of SIQPII and the ions of the NaCl had photocatalyzed the QHIn in 28 min. Hence, SIQPII was intimately aligned in a close vicinity of QHIn to minimize a QEB. The SIQPII with a maximum Raman intensity unlike I and III with the electrolytes has enhanced a PCR with high Φ, whereas the SIQPIII having ERG had generated a robust outgrowth due to a synchronization unlike II with EWG ( Figure S3(b,c)). The SIQPIII with a robust upward growth has probably accumulated the electrolytes and QS taking a longer time than II for PCR. The ERG without Raman D and G peaks 1 did not robustly catalyze the PCR compared to EWG. The homogenized charged sites with the least surface forces of SIQPIII had generated a straight line in Raman spectra 1 and is self-engaged for occupying the residual forces unlike II that responds to hv with highest Φ. The aligned surface charges of SIQPIII compared to II infer less crystallinity 1 and are FT-IR active due to bending frequencies compared to SIQPI and II. The SIQPII reengineered its functional sites with Na + and Cl − ions to PCR QHIn.
2.4. FT-IR Analysis. FP delocalizes the electron toward its center rather than a prompt response to receive hv delaying a PCR compared to II and III ( Figure S4(a)). The CN withdraws the electron clouds from phenyl, and the NO 2 withdraws the electron clouds from NIQ, so SIQPII bonds are stretched. The NC-phenyl, 2NC-pyz, and NIQ stretched in FT-IR ( Figure  S4(b)). The ERG and H 3 CO-phenyl of SIQPIII tilt the electron cloud toward CCA while the 2NC-pyz and NIQ have counterbalanced the electronic charges ( Figure S4(c)). Thus, the covalent bonds could not generate bending in FT-IR ( Figure  S4(c)). The sharper peaks are noticed in the bending domain with SIQPIII than II and I due to synchronization. The molecule is engaged in C−C sites rather than stretching and has negligibly induced the stretching peaks from 2250 to 4000 cm −1 ( Figure  S4(c)). The bending of ERG does not favor photocatalysis and differs in FP, NC-phenyl, and H 3 CO-phenyl. The photocatalyst with maximum number of EWG could lead to PCR-persistent pollutants.

QHIn PCR with Photocatalyst SIQPs and Cocatalysts
NaCl and KCl. The e − and h + holes could not reduce QHIn without electrolytes as these have hydrolyzed a mixed solvent generating the H + and − OH and ψ SIQPs and ψ dyes . The 0.01 mmol SIQPs with 0.01 × 10 −3 % μg/v aq-GO and 0.01874 mmol aq-MB were separately prepared for PCR. Then 0.01 mL of MB was    The absence of MB dye in effluents was confirmed by using UV−vis. GO as a cophotocatalyst intensified the ψ SIQPs with a larger surface area (SA) on acquiring a lower activation energy (ΔE a ) for a higher Φ as in eq 1.
Here, K SA is the SA constant, and the monodispersed SIQPs and dyes have generated ROC using the least ΔE a generated holes with intense ψ and π conjugations that may hinder ψ SIQPs ( Figure  S5(a)) as where E ψ is the energy of ROC via e − and h + holes at a specific wavevector maintained a lattice, with KE (p 2 /2m), PE (q SIQP + × q dye − /4πεr 2 ) at r, nm, and ε is the permittivity between the SIQP and dye (eq 2). The e − and h + holes of ψ SIQP with GO and electrolyte reduced �S + − of MB. The SIQPs, despite bonding with the FP, CN, and OCH 3 and having delocalized phenyl, one, and two nonbonding electron pairs, respectively, could not reduce the QHIn. Neither the SIQPs alone nor with GO could PCR the QHIn (Figure 4(b)). The SIQP with electrolytes monodispersed the dyes (Figure 4(c)). The QS having alternative double bonds with CCA created a lot of hindrances to minimize QEB due to their EER. The electrolyte interacts with the EER sites to attract the electron cloud toward its ionic charge ( Figure 5). Hence, SIQP alone did not act as a stronger pointed charge, and the Na + point charge undergoes EER to align with ψ SIQPs that had destabilized the QHIn with 0.1 mmol aq-NaCl of 0.1 ionic strength (I) as in eq 3.
The NaCl has weakened the double bond of QHIn and SIQPs both with a robust ψ S developing PCI as the OH − + H + pushes the Na + toward a negative charge of QHIn ( Figure 5 and eq 4).
The e − and h + holes reduce the residual charges of QHIn illustrated as The H + ion is simultaneously consumed but NaOH could not reduce QHIn. The internal exchange of the ionic species might have excited the electronic activities without interacting with the delocalized charges (eq 5). The NaCl is hydrolyzed to NaCl + H 2 O → NaOH + HCl, but NaOH with common Na + inhibits a hydrolysis that might have disrupted the QS (eq 5). The Cl − might have disrupted the H bonding forming anionic 17 hydration sphere (AHS) on the surface attracting the cation hydration sphere (CHS). These establish a closed contact of the e − and h + holes with QHIn. The NaCl and KCl have

ACS Omega
http://pubs.acs.org/journal/acsodf Article monodispersed a biphasic solvent holding aq-QHIn-NaOH at NTP by lowering ε for QHIn with SIQPs. The two experiments were conducted to photocatalyze the QHIn for finding a role of QS. The SIQPs with GO reduced MB in 110, 27, and 55 min unlike 120, 45, and 70 min alone. SIQPI, II, and III with NaCl have reduced the QHIn in 120, 28, and 50 min, respectively, to PCR a persistent QHIn. 18 The CHS and AHS shielded a QHIn from the medium to reduce it over a longer time. The water solubilizes the EtOH and QHIn both to a single phase, and the SIQPs are soluble in ACN, developing a second phase without NaCl. The Na + of NaOH could not disrupt the H bonding as Na + and Cl − had mutually monodispersed the EtOH, water, QHIn, and SIQPs to a single phase ( Figure 5). The SIQPs reduced MB but not the QHIn without electrolyte as DRET failed to reduce QHIn which has no charge-deficient sites. Had the Na + and Cl − counterbalanced the e − and h + holes then there would have not been any color change on subjecting them to hv. So, a color disappearance on receiving hv infers QHIn reduction to HIn at pH 8. The − OH and H + produced H 2 O, leaving Na + toward e − charged QS, but NaOH could not interfere with QHIn reduction except with SIQPs as a reducing agent. The concentrations of QHIn as an oxidizing agent and of SIQPs as a reducing agent depend on production and consumption of e − and h + holes, respectively (eq 6).
h QHIn(ox. ) pink SIQPs Na benzoate salt(red. ) colorless SIQPs The BaCl 2 , a weak electrolyte, could not weaken the QS compared to a Na + with an effective nuclear charge interacting with ψ C=C of QHIn ( Figure 5). Thus, an electrolyte with shorter size assists SIQPs to photocatalyze the QHIn with a small ΔE a . The NaCl developed PCI with QHIn and with the respective constituents of SIQPs to disrupt the H bonding ( Figure 5). The KCl with similar sizes of K + and Cl − developed a small ζ with comparatively weak H bonding disruption on canceling out charges on ions to reduce QHIn in 138, 58, 63 min, respectively, compared to NaCl. The Cl − , a common anion of NaCl/KCl, could not compensate for a cationic charge. The ψ CHS and ψ AHS as a shorter sized Na + with stronger nuclear charge unlike K + weakened the QS (Figure 6(a,b)).

Mechanism of SIQPs to PCR the QHIn.
The ψ of water and ACN accommodate hydrophilicity and hydrophobicity of SIQPs to minimize a QEB for QHIn, BBR, MO, and transition-   (Figure 7).  Figure 11). The e − and h + holes of GO might have mutually counterbalanced the SIQPs resulting in no photocatalysis ( Figure S6 and S7). The SIQPII alone produced ∼5 times higher Raman intensities than I and III and reduced the QHIn in 28 min with electrolyte. The ψ 2NC-pyz interconnects the NC-phenyl via CCA of −CH of pyz where its density of energy state (DOS) restricted its alignment toward NIQ as CCA is bonded with 1C, 2C, and tertiary N atoms of pyz, respectively. The CCA with SIQPII regulates the ψ 2NC-pyz by mildly blocking the electron clouds of 2NC and CN for reaching NIQ to weaken the EER. Compared to 120 and 50 min for QHIn PCR by SIQPI and III, the II has reduced in 28 min, and ∼3 times the DOS of its 2NC and CN might have mutually been interconnected with longer MFP. The 2NC and CN might have produced the maximum holes in a similar phase but still the SIQPII could not reduce QHIn ( Figure 11). MNPs activated holes of the SIQPII for QHIn PCR as the Fe 3+ and Fe 2+ oxidation states could reorient the NC-phenyl and 2NC-pyz to reduce QHIn in a shorter time as it took 48 h instead of 28 min (Figure 11). Though the NaCl 19 was common in both, the MNPs have hindered a PCR of QHIn similar to an inhibition of a drug release from the trimesoyl tridimethyl malonate vehicle. MNPs with SIQPs have delayed @ PCR acting as an antiphotocatalyst, needed for stability of color coating in thin films. 20 The UV−vis abs by SIQPs for reducing QHIn with electrolyte KCl before and after photocatalysis are negative within 230−320 nm. As the CH 3 −C δ+ �N δ− and H δ+ − O δ− −H δ+ both compete to interact with the K + and Cl − to disperse the QHIn and SIQPs equilibrated by CH 3 CH 2 OH where the hv of visible range reorient the QHIn and SIQPs to optimize in mixed solvent and align the dipoles on releasing the energy with transmittance >100% light on absorbing energy from a system. Thus, it attains a negative abs enhancing a PCR, as the aligned dipoles prevent a recombination of holes. The negative abs infers a constructive role of the electrolytes for enhancing a PCR. The LPE of O atoms of H 2 O and CH 3 CH 2 OH and of the N atom of ACN expeditiously respond to the UV light upon absorbing it. The KCl is dissociated into K + and Cl − ions and activated a H-bonded H 2 O structure, causing a transition. The LPE are embedded by KCl due to the ionic hydration spheres of K + and Cl − and need more energy for UV light passage. The energy released on aligning the solvents induces molecular reorientations by taking energy from the system as an endothermic process. The electrolytes via cation− anion interactions reoriented using the energy of a system with resultant negative potential energy. No negative abs with SIQPs alone and with QHIn dispersed with mixed solvent except with electrolyte. Thereby, the solvated structure with salts inducing the maximum reorientations require exceptionally higher energy within 200−230 nm, which is taken from the system itself. It withdraws a higher energy from a medium leading to negative abs in UV. Generally, endothermic chemical processes are studied with TGA. Going forward, it could be studied with the UV light abs. The mixed solvent induces maximum reorientation motions like rotational, vibrational, and translational with the QHIn molecules vis-a-vis SIQPs as no complex formation is developed. Had a complex been developed there would have not been a PCR. The chosen mixed solvent does not coagulate, cluster, or defunct any of the molecular species. The monodispersing solvent reorients QHIn and SIQPs on utilizing a maximum energy from a medium producing a negative abs.

UV−vis Study PCR Dyes by SIQPs with NaCl/KCl
2.5.4. Fluorescence Analysis. Fluorescent 1 spectra produced the highest intensity (I f ) 13995 au with SIQPII at 490 nm unlike 167 and 65 au at 490 and 489 nm with I and III. SIQPI developed a sharper and milder peak intensity due to delocalized FP. The EWG/CN SIQPII smoothed the surfaces but the ERG/ OMe with III created chaos as CCA could not harmonize ψ. The cocatalysts excite electrons of QHIn and SIQPs to reduce QHIn. The fluorescence for HIn, QHIn, and electrolyte is examined with varying concentrations to study the electronic effects. Hence, at 320 nm, an excited wavelength (λ exc ), the emitted wavelengths (λ em ) 408, 383, 466, and 465 nm distinguish QHIn, HIn, NaCl, and KCl, respectively, via I f and Φ activities ( Figure  S8 and Table 3). Increasing the HIn concentration has produced sharper peaks upon increasing I f with a stronger hv interaction compared to QHIn (Figure S8(a)). The sharper intensity with HIn, unlike that defused with QHIn, varies with its concentration at the same λ max (Figure S8(b)). The diffused peaks predict the QHIn oscillations with different ψs compared to the integrated electronic state of HIn. Hence, the photo-catalysis to degrade the QS is justified. In QHIn spectra with the same peak of lower I f , and new broader peaks at 375−475 nm infer unphotocatalyzed QS ( Figure S8(b)). The QS undergoes splits by NaCl from 400 to 650 nm that destabilize a QS at lower I f as no split in QHIn without electrolytes occurs contrary to multiple splits with electrolytes ( Figure S8(c)). These have quantized the PE to many domains with higher I f ( Figure  S8(b)). The concentration trends of I f with QHIn remained stable and changed on varying NaCl concentration. Quasi-TS (transition state (TS)) with NaCl infers anharmonic oscillations but with the KCl no split occurs except for a drastic change ( Figure S8(c,d)). The shorter sized Na + unlike a larger sized K + has weakened a solvent bonding with QHIn due to a common Cl − anion ( Figure S8(d)). The NaCl enhanced the Φ as a shorter Na + induced oscillations compared to smoothing with the KCl. The charge on K + is q K + and on the QS − is q QS − , . For K + , the ε of the medium is reduced due to a large sized cation compared to Na + where it interacted with the medium as well as with QHIn. The continuous oscillations unlike KCl have lowered the ε; however, the ε with NaCl is mutually equilibrated (>r). A quasi-TS favors the higher oscillations with NaCl than KCl. The ε for the specific ratio of NaCl and KCl could further reduce a PCR time. The study is continued with a shorter sized Li + cation having larger ε to further reduce a PCR time as a large sized Ba 2+ cation could not PCR QHIn but rather was settled. Thus, the cationic interactions contribute toward photocatalyzes QHIn. The KE with electrolytes elevated a polarity for photocatalysis, and fluorescence has illustrated their ionic actions. A single peak at 480 nm with two other peaks infers vibrant interactions of NaCl ( Figure S8(c)). Fluorescence of QHIn and SIQPs inferred the induced cation selective activities with NaCl to split PE of QHIn and SIQPs for photocatalysis. The NaCl was interfaced with the SIQPs and QHIn unlike BaCl 2 that did not interface a medium due to the larger Ba 2+ size ( Figure S9). The NaCl and SIQPs were recovered after PCR and were washed with chilled aq-EtOH. NaCl reduced athe bandgap of QHIn and SIQPs to generate the constructive oscillations in fluorescence ( Figure   Figure 11. Electronic mechanism of MNPs undergoing QHIn photocatalysis by SIQPs.  (Figure 12). A smoothed curve at 425 nm with higher concentration favored a PCR (Figure 12(a)). NaCl with FP developed an integrated peak at 425 nm and with CN detained one peak at 425 and another at 520 nm with high I f value. NaCl might have stressed the CCA of SIQPII producing peaks at 425 and 520 nm unlike a single peak at 425 nm with FP. The break without NaCl expands smoothly at 489 nm (Figures 12(a,b)). The SIQPII with NaCl generated a new peak due to the second transition, and it responds at 520 nm due to phosphoresce, contrary to I and III ( Figures 12(a−c) and (e)). The NC-phenyl in SIQPII expands from CN as the terminal NO 2 of NIQ shifts away an electronic cloud with phosphoresce unlike FP and OMe. Thus, the TS formation with NO 2 and QS of O atom decolorizes QHIn (Figure 12(e)). The OMe activity is counterbalanced by 2NCpyz and NO 2 without generating an extra peak due to interaction of the ion with the QHIn to produce a single peak ( Figure  12(c)). The NaCl with SIQPII generated a phosphorescence with a conjugated QS that shortened the reduction time unlike with MNPs. The MNPs have produced a broader intensity peak and oxidation potentials of Fe 2+ and Fe 3+ that destabilize PCI and QS linkages with the Na + ion (Figure 12(d)). MNPs with two oxidation potentials have caused a mild haphazardous environment that has stabilized the scintillations and could not   produced a broader fluorescence curve due to unaligned charges ( Figure 12(d)). Electronic properties of MNPs with NaCl suppressed the photocatalyzing activities on counterbalancing the oscillations. A hv continuous hv absorption could have slightly aligned the charges in 48 h, and a peak at 500 nm is sharpened and synchronized. The studies are continued with ZnO for shortening the PCR time. The I f and Φ for SIQPII +MNPs, SIQPI, II, and III with NaCl are calculated ( Table 3).
As Φ is a ratio of n e to n a , Φ % for SIQPI with NaCl (eq 9) is The Φ% for SIQPII, III, and the II+MNPs with NaCl are calculated as Φ SIQPI+NaCl = 76.7%, Φ SIQPII+NaCl = 75.6%, Φ SIQPIII+NaCl = 72.0%, and Φ SIQPII+MNP+NaCl = 73.4% (Table  4). The Φ% for QHIn, HIn, NaCl, and KCl are calculated with eq 9 as Φ QHIn = 78.4, Φ HIn = 83.5, Φ NaCl = 68.8, and Φ KCl = 68.8% (Table 4). The 83.5 and 78.4% highest Φ values with HIn and QHIn infer delocalized and QS stability, respectively. The negligible I f values for SIQPI with NaCl reduced QHIn in 120 min as it had equilibrated the charges unlike 28 and 55 min with II and III. The NaCl potentializes SIQP functionalized with EWG and ERG, respectively. The electronically integrated SIQPI produced negligible I f values and reduced over a longer time. The SIQPs with ERG and EWG enhanced a maximum I f by disrupting a delocalization unlike FP. The electrolytes vibrantly influenced the scintillations of EWG and ERG via π → π* and n → π* transitions; e.g., the higher I f values for SIQPII and III compared to I with NaCl produced the highest Φ in the same sequence of PCR with the QHIn. The CHS and AHS adhered to SIQPII and EtOH would have produced the higher electronic activities of NC-phenyl compared to I and III with FP and OCH 3 (Figure 13(a−c)). The NC-phenyl robustly responded to laser light and the ψ strictly infers the electronic environments of pyz and NIQ. SIQPII and III having NCphenyl and H 3 CO-phenyl have generated ψ NC-phenyl and ψ Hd 3 CO-phenyl as EWG and ERG activities have caused a mild stretching with pyz and NIQ (Figure 13(b,c)). The NC-phenyl with homogeneous electronic activities produced an intensified ψ harmonized . The electronic environments of pyz and NIQ with SIQPII could not cope with the NC-phenyl by channelizing its energy to 2NC-pyz and NIQ via CCA. The NaCl has aligned the ψ 2NC-pyz and ψ NIQ . The CCA with SIQPII may not support reversibility of ψ NC-phenyl ≠ ψ 2NC-pyz ≠ ψ NIQ mutually due to different electronic states that attract the NaCl (Figure 13(b)). The CCA as a stabilizer with higher PE and lower KE led to With CCA, the KE = 0, so eq 10 becomes E q q r 4 2 = + . The energy (E) could be of pyz and NIQ as a NaCl with respective ions stabilizes the secondary and tertiary TS with deficient electronic oscillations. The NC-phenyl acted as the ground state (S 0 ) and the CCA as the secondary state (S 1 ) to optimize a tertiary (S 2 ) state ( Figure 13(b)). The CCA ≈ NIQ could generate S 2 which might be supported by CCA ≈ pyz to develop a full fledged electronic system based on Schrodinger's eq 10 rearranged with KE> PE as eq 11.
Stretching S 2 emits electron as its PE is converted in KE due to HOMO → LUMO to equilibrate ψ of SIQPs expressed as NIQ ≈ CCA ≈ pyz.

PCR of BBR by SIQPs.
SIQPs have reduced 100% MB and BBR despite a double number of conjugated rings with BBR compared to MB. Initially, a blue color of BBR with SIQPI and II in aq-ACN reduced to colorless after 62 and 46 min, respectively ( Figure 14 and Table 5). The SIQPIII with an O atom of OCH 3 took a longer time as its electron-releasing activities caused EER with a delocalized phenyl ring influencing both the pyz and NIQ templates. The BBR with π-conjugated rings created a center to receive the hv and created the possibility of energy loss. It activates the centers that do not resonate with the same energy and may lead to EER and the SIQPIII having OCH 3 and BBR with delocalized rings, ethyl groups, with two SO 3 2− delayed @ PCR. The quaternary N with alternative double bonds of BBR and a CCA delayed a PCR affecting an overall delocalization. The BBR with an active core center activates all three different sites. A delocalization is extended to periphery, probably many electronic sensitive sites on receiving hv from SIQPIII reorient, align, and oscillate to acquire energy for PCR. Unlike MB, the BBR with a flexible electronic configuration does not act as a harmonic oscillator with different ψ. Thereby, most of the energy received by SIQPIII is transferred to BBR on a resonating ψ as it aligns and reorient to PCR a dye. The complicated

The pH (4 and 8) and T Effect on PCR of BBR by SIQPI.
Aq-BBR alone at pH 4 was reduced in 110 min unlike 180 min with SIQPI and acted as a negative photocatalyst ( Figure 14 and Table 5). The BBR and SIQPI with their respective FGs and π conjugation might have engaged the e − receiving centers for generating a hole mechanism. aq-BBR alone at low pH received hv directly and was reduced in a shorter time due to the π conjugation sites. Their π conjugated rings with two ethyls, a delocalized ring, and electron-deficient N might have developed the resonating holes. The blue color of aq-BBR at low pH disappeared in 110 min as the H + ions have replaced its Na + of SO 3 2− . The Na + might have interacted with the Cl − of BBR, and the e − holes interacted with its quaternary N atom where a double bond of delocalized ring might have shifted toward a quaternary N atom. Also, the Na + could have developed the PCI to disrupt the delocalized ring of BBR. The SIQPI with BBR seems to hold the H + ions by H bonding with its NO 2 and π conjugated e − clouds resonating in different phases. No H + ion is free to hold the electronic sites of BBR and could not destabilize the quaternary N atom. The π conjugated systems with FEs of BBR and SIQPI both could have mutually doped and develop a stable nanocluster. Thus, the SIQPI and BBR mutually might have generated the resonating energy forming a compact nanocluster and aligns their electronic configuration that remained suspended homogeneously in water ( Figure 14). Thus, the SIQPI and BBR might have developed the electronic linkages resisting PCR activities. The hv could not be absorbed by a nanocluster, so the SIQPI acted partially as an adsorbent than a photocatalyst at a pH 4.
T Effect on BBR PCR. The SIQPI at ∼3°C reduced the BBR over a longer time. At ∼3°C, a milder resonating energy of SIQPI developed a weak ψ so a higher E a is needed to resonate ψ and PCR. It has delayed a PCR process (∼5 min) to overcome QEB contrary to a shorter time. At pH 8, a BBR alone was reduced in 36 min compared 15 min with SIQPI. The BBR with SIQPI at normal T and pH 8 was reduced in 15 min compared to 20 min at ∼3°C (Figure 14). The T catalyzes the generation of holes; however, the SIQPI with NaCl at pH 8 was photocatalyzed aq-BBR in 5 min. Hence, a NaCl reduced a dye in 1/4 the time. Therefore, a catalysis of dye with electrolyte is a greener route where the Na + attacks the Cl − of quaternary N as well as initiates the PCI with their π conjugated systems. The − OH controls a PCR of BBR by destabilizing a structured solvent and PCI. At lower pH, either a free radical or water could have split as H 2 O → 2H + + O 2− . At pH 4, a water splitting could have been inhibited due to a common H + ion unlike at pH 8, so it is an essential mechanism at low and high pH due to H + ion concentration. For adsorbing any industrial dye by SIQPs, a pH range is a perquisite with SIQPs photocatalysts under SL at pH 4. The Na + , a common ion at pH 8, did not affect PCR unlike at pH 4. The SIQP as photocatalyst and NaCl as a cocatalyst at higher pH enhanced the T oscillation the electron where the Na + and Cl − catalysis generation is due to the electronic environment around the SIQPs.   Figure 15). The SIQPs with MO increased a delocalization by shortening the PCR time. The 0.02 mL of 0.01 M NaCl with SIQPI, II, and III individually has further lowered the MO reduction time to 19, 12, and ∼1−2 min ( Table 5). The electrolytes monodispersed at pH 8 for a better response of hv. The Na + of NaCl and a Na + of NaOH might have counterbalanced a pH effect. Thus, the MO was degraded in  (Table  6). SIQPs are highly stable at high T compared to the metal complexes. The metal complexes are not recycled for reuse as they undergo structural transition by losing photocatalysis abilities as compared in Table 6. SIQPs have reduced QHIn, BBR, and MO and were maintained structurally with the reducing activities for receiving the hv at various T and pH. The SIQPs have worked with several solvents like ACN, aq-ACN, and aq-ACN-EtOH with electrolytic solutions enhancing PCR of dyes. SIQPs were reused for four successive cycles to degrade the persistent pollutant due to their survival. The SIQPs worked without acquiring any transitional/structural changes. SIQPs have physiosorbed the dyes without chemisorption on reduction so their surface area and surface energy remained almost the same in each reusable step. Their PCI interactions with NaCl, KCl, and MNPs are weak and do not concentrate the negative electronic charges on the benzene ring of SIQPs. The EWG regulates the PCI interactions with any of the ions, and their electronic cloud is not nucleated to a center. The PCI could develop with QHIn but not with CCA having different functional units. The CCA seems to generate the anti-PCI activities to avoid their degradation. The SIQPs as novel photocatalysts reduce the dyes in the presence of NaCl, KCl, and MNPs by maintaining a maximum hv receiving activity. The MNPs were settled at the bottom but with electrolytes were dispersed. Thus, the SIQPs did not participate in the disruption of medium linkages with a least solvent−MNPs interaction. The MNPs were phased out and could not communicate with dye and remained unengaged, but with electrolytes, their different oxidation states equilibrated with respect to oxygen. The SIQP could not disperse the MNPs as the SIQPs structure is integrated via CCA. The SIQPs have developed an extended conjugated electronic cloud throughout a molecule. Thus, there is no SIQPs interaction between medium and dyes rather than developing the PCR activity with electrolytes without SIQPs degradation. SIQPs with increasing concentrations linearly increase the intensity in fluorescence confirming their nondegradation.

PCR of Transition Metal Salts with SIQPs.
Aq-NiCl 2 (light green), aq-CrO 3 (red), aq-KMnO 4 (purple), aq-CuSO 4 (blue), and aq-MnCl 2 (light pink) were reduced by SIQPII with a highest @PCR due to its N�C-phenyl ( Figure 16). The transition-metal ions caged with ionic hydration spheres interfered with a PCR. The caging was disrupted by sonication for a specific period and T at @30 kHz. Their UV−vis were recorded at initial and final stages for calculating the E a with Arrhenius eq 12.
The A is the pre-exponential factor as hv generated by SIQPII to reduce the metal ions or form a MOF, 24 R = 8.314 J mol −1 K −1 , and t soni is sonicated time. Abs = f(t Soni )) is plotted vs (1/ t Soni ) with E a /2.303R as the slope value and the R value, the E a is calculated with eq 13. The E a (J/mol) is calculated as (KMnO 4 +SIQPII) 1822.00 > (CrO 3 +SIQPII) 1315.65 > (MnCl 2 +SIQPII) 556.34 > (CuSO 4 +SIQPII) 419.37 > (NiCl 2 +SIQPII) 349.22 and infers a higher E a for aq-KMnO 4 +SIQPII than other transition-metal ions ( Figure 17). The trend infers a lower activity due to 4O 2− with K + and Mn 7+ , and the Mn 7+ is reduced to Mn 2+ of black color. The O 2− anion released electrons to reduce Mn +7 + 5e − → Mn +2 + 2e − → Mn 0 as an in situ double reduction process. Thus, reduction of KMnO 4 has utilized an evolved energy to PCR in 30 min unlike other transition metals. The e − holes generated by SIQPII convert a nascent O atom to O 2 that generated a high pressure and opened the lid of a PCR vessel. The SIQPII reduced KMnO 4 to prepare the Mn NPs as Mn +7 + 5e − → Mn +2 + 2e − → Mn 0 and formed nascent O atom from O 2− electrons. The O atom quickly received the e − holes so a SIQPII did not allow a reversible reaction of KMnO 4 . The second highest E a for CrO 3 infers a stronger chemical activity due to a lower number of O atoms with a single Cr 6+ unlike 4O 2− , K + , and Mn +7 of KMnO 4 . Initially, the SIQPII with CrO 3 produced a red turbidity that transformed to a brown color in SL and settled at the bottom. The central Cr 6+ (4s 0 3d 0 ) shared its valence d electrons and got adsorbed with SIQPII to develo a MOF. The SIQPII adsorbed the Cr 6+ pollutants from industrial wastes. 25 In addition, the MnCl 2 with Mn 2+ with d 5 is stable and has developed MOF of a dark gray color and was settled at the where E = energy, k = Boltzmann distribution constant, K T = Kelvin T constant, h = Planck constant, e = oscillating electron, V = electric potential, and ν = frequency. The ν of differential wt loss depicted sharper peaks at K T calculated with eq 14 ( Figure  18 and Table 7). The wt loss elucidates a preferential thermal stability of each constituent. The water released during SIQPI synthesis might have developed an azeotrope with SIQPI cavities and separated at >110°C ( Figure S10). The azeotrope Figure 17. UV−vis abs spectra before and after PCR of transition metals by SIQPII.
attached either with cavities of 2NC or NO 2 affecting a sharper activity via various electronic motions on raising the T. The optimized SIQPs are dislocated by twisting the rotation and vibration of bonds where the hv on receiving heat elongates a bond of FG as per Hook's law. 26 These activities caused a wt loss with ΔH/K T , the ΔH = Δq, a thermal content at constant pressure. The SIQPI at 108°C slightly released heat but at 190− 290°C broadened a peak on a heat loss ( Figure S10). Initially, a where ΔG = Gibbs free energy, 27 n = number moles in wt loss at K T , R = constant, and ν = frequency of electrons at transition peaks. Increasing T induces the TS and at K T with @ wt loss. The ΔG 28 is calculated with eq 15 using K T and R values, and the n is calculated in eq 16. Both the ΔG and n values for each TS are calculated for bond breaking at a specific wt loss ( Figure 19 and Table 7). The π conjugation of FP and NIQ of SIQPI has extended delocalization caused by NO 2 as a major exothermic curve at 220°C. The CCA may not permit FP delocalization, but due to a similar phase of the π conjugations, the ψ might still have overcome QEB at 220°C. On continuous heating, the SIQPs acquire energy ΔE a for a wt loss. ΔE a along with ΔG is calculated by fitting wt loss vs T in Arrhenius 29 eq 17.
The C atom of pyz with 2NC has a single covalent bond so no electron cloud was affected. The multiple activities of SIQPII influence the ψ with specific ΔC p @ 22 μg/min wt loss at 250°C. The μg/min, a @ wt loss vs T, is lower as heat generates the internal TS with S 1 to engage the SIQPs rather than a wt loss ( Figure S10). The exothermic heat with ERG/OCH 3 has caused a sharper curve as OCH 3 develops its own motions rather shifting its electron cloud toward delocalization. The OCH 3 as a single domain generates its own ψ despite an oscillation of 2NC at 230°C. The OCH 3 aligns delocalizing activities to a sharper exothermic curve jointly at 230°C along with its own oscillations ( Figure S10). The exothermic curve at 270°C infers an optimized OCH 3 oscillation and delocalization together with 2NC and NO 2 FG. The NO 2 , 2NC, and phenyl affect @wt loss on raising a T, whereas delocalized FP bonded with pyz acted as a free unit. The CCA may selectively allow the robust ψ affecting delocalization of NIQ. Thus, a CCA with QEB may filter the weak ψ of respective units; e.g., had CN been absent then a major exothermic curve could have been repeated as SIQPI does not have CN with FP ( Figure S10). The extra exothermic curves with SIQPII as CN need energy for oscillations so on further heating the II has weakened the binding forces. SIQPI is a stronger heat dissipator than II and III and may be used in IC/electronic systems for heat dissipation. The CN generates a first exothermic curve at 230°C and second at 320°C (Figure S10(b)). The CN triple bond was quenched and restricted oscillatory motions of phenyl at 300°C. The two closely placed splits infer domains of 2NC and CN at a closure distance to project their impact together; still, a smaller impact of individual CN is depicted with small two peaks ( Figure  S10(b)). Had the 2NC been together, it could have produced a major impact but these 2NC are not connected to delocalize a phenyl preventing the oscillations. The CN has sharpened the phenyl activity by dissipating the heat that further split the peaks. SIQPII with CN and the III with OCH 3 have caused the additional split which are missing with FP of I except a single curve. The CN of SIQPII split its overall electronic activities as the S 1 or tertiary transitions (T 1 ) in photoluminescence minimize a wt loss at a lower @. Initially, the SIQPII due to an interrupted delocalization with CN generated multiple small curves at low T. The small curves disappear with rising T within a short time. The NO 2 and 2NC both have sharply split into curves whereas the phenyl with EWG/CN and ERG have disarrayed. The small splitting is produced by heat-sensitive SIQPII and III from 400 to 450°C as a heat sensor. The heat generation and dissipation are of the same orders with closely placed transitions. SIQPI with a single ΔG SIQPI at 110°C, on further heating, stabilizes the molecular motions at 230°C. SIQPI at 230°C has produced a single major peak unlike multiple peaks with II and III due to a stabilized T response. The SIQPII and III distinguish the CN and OMe as the CN generated two TS ( Figure S10(b,c)). The NC-phenyl and 2NCpyz of the SIQPII slightly caused the same influence mutually as the CN stabilized domain does not affect its Lennard-Jones potential. Interacting activities of three sharped peaks of CN with SIQPII have strongly developed the Born−Oppenheimer approximation 30,31 compared to III as the N atom of CN with sp hybridization mildly influences a delocalized phenyl via a delocalized electron cloud (DLEC) that infers a T-sensitive broader peak ( Figure S10(b)). The 2NC had generated a broader peak at 325°C in alignment with the NC-phenyl to influence the DLEC and activities of 2NC. The OCH 3 with hydrophobicity minimized a split between the peaks due to EER of O atom with DLEC with the maximum collisions in SIQPIII ( Figure S10(c)). Also, an increase in @wt loss from 21 μg/min with EWG and 62 μg/min with ERG infer the II as a stronger photocatalysing sensor ( Figure S10). The ΔG SIQPs values are calculated from the wt loss to infer spontaneous photocatalysing activities. The ψ CN , ψ 2CN , ψ Pyz , and ψ NIQ of SIQPII have reduced a QEB where the e − and h + holes photocatalyze 31 dyes. The closely placed sharper splits infer the electronic oscillations of the 1a C atom of pyz bonded with 2NC and another C atom of 2NC. The oscillations of 1a C atom of pyz differ from the 2 and b C atoms of phenyl along with a C atom of CN. A major broader third peak with a lower wt loss infers an equilibrated SIQPII structure as on raising a T. SIQPII with EWG reorients at 320°C compared to I and III at 240 and 270°C, respectively ( Figure  S10). The delocalized electrons and ERG both move along the pyz and NIQ causing EER with KE (p 2 /2m) unlike EWG developing PE (q + q − /4πεr 2 ) which aligns the holes of SIQPII compared to (p 2 /2m) that weaken hole alignments of I and III.
2.7. Differential Scanning Calorimetry (DSC) Analysis. NIQ with > CO and NO 2 on heating split at ∼207 and ∼253.8°C utilizing −0.0161 and 3.1180 J/g ΔH, respectively for their its electronic reorientation ( Figure S11(a)). A major break up at ∼308.4°C with 98.33 J/g ΔH infers a disruption of van der Waals within NIQ due to DLEC and N atom with extended delocalization. The sharper peaks infer manifolds delocalizing rings and EWG NO 2 ( Figure S11(a)). The sharper peaks of SIQPI 32 from 31 to 38.2°C and 38−72°C infer a sharper lattice reorientation ( Figure S11(b)). The SIQPI is reoriented, so no unused heat is generated, but from 83 to 100°C the 23.43 mW energy is released. The robust reorientations might have oscillated to partially increase the heat as ROC infers HOMO ⇄ LUMO. The HOMO → LUMO ⇄ LUMO → HOMO cycles develop a sharper HOMO → LUMO cycle with SIQPI ( Figure S11(b)). Initially, HOMO → LUMO activities are stronger from 120−225°C where HOMO → LUMO equilibrates with equal LUMO → HOMO cycles. SIQPs abruptly collide with KE = kT expressed as in eq 18.
A rominent DSC exothermic peak is minimized as EWG with SIQPII sharply has reoriented the DLEC ( Figure S11(c)). A straight line from 125−200°C infers no T effect as the CN have disrupted the ψ h + and ψ e − to intensify the ROC in SIQPII, whereas no ROC generated from 130 to 200°C except a mild split at 120°C on increasing T and electronic (ψ n → ψ n* , ψ π → ψ π* , and ψ σ → ψ σ* ) transitions of NC-phenyl to minimizing QEB via CCA of SIQPII. The ψ of FP with ψ π → ψ π* and ψ σ → ψ σ* mutually counterbalanced the energy without increasing the T. On raising the T, the ψ population are counterbalanced in the same ratio, so no extra energy is attained up to 210°C ( Figure  S11(c)). A continuous electronic transition of the respective domains generates ψ that may phase out due to EER utilizing their energy sharply. These activities generate a downward peak at 278°C as the CCA could induce excessive rotations and vibrations of pyz and NIQ on acquiring energy. The broader peak from 225 to 320°C infers ψ pyz ≠ ψ NIQ templates as their energies largely differ. With SIQPIII, an ineffective broader peak with a localized milder split is generated at 90−110°C. The OCH 3 via phenyl resisted −O− electron mildly influence DLEC, and a milder peak at 92°C is generated. The OCH 3 contrary to CN generates electronic transitions at 278°C. From 190 to 275°C, a decrease in heat flow occurs slowly compared to EWG, i.e., CN ( Figure S11(c,d)).
2.8. Density Functional theory (DFT) for Analyzing Electronic Potential of SIQPs. Quantum mechanical simulation of holes of SIQPs and NIQ have been estimated by fitting G09W at the B3LYP/6-311++G (df, pd) level 33 ( Figure  S12). Their optimizations were verified in the absence of negative frequency where Koopmans theorem has determined ionization energy (I) and electron affinity (A) via HOMO and LUMO transitions as I = −E HOMO and A = −E LUMO . Here electronic chemical potential (χ), global hardness (η), electrophilicity 34 (ω), and a maximum charge transfer index (ΔN max ) were calculated using DFT 35 GaussView 6.0.16 software was used calculate HOMO and LUMO energies with MEP graphs of SIQPs 36 and NIQ for their active intramolecular interactions (Table S2). The ΔE gap (eV) as SIQPII (3.5193) > I (3.4586) > III (3.2469) infers the stronger interactions of EWG with dyes in a shorter time. The μ and η values (eV) as SIQPII (−5.2928) < I (−5.1027) < III (−4.9522) and SIQPII (1.7596) > I (1.7293) > III (1.6234), respectively, infer the II with NC-phenyl as a robust photocatalyst. The ω and dipole moment values infer higher electrophilicity index and dipole moment of SIQPII. The polarizability index (ρ a.u.) as III (412.3949) > II (411.3741) > I (391.2703) of SIQPII and III with CN and OCH 3 , respectively, is higher than that of I. Electron density and surface analysis were simulated with the molecular orbital to infer an interactive region higher with SIQPII ( Figure 20). The HOMO density with NIQ is localized on a central five-membered ring and partially on the O atoms of

ACS Omega
http://pubs.acs.org/journal/acsodf Article substituted NO 2 while the LUMO exists on surfaces. Molecular electrostatic potential expressed by dark red color infers an active site of SIQPs for their electrophilic and nucleophilic activities, respectively. The CN 37 is favored over O atoms of NO 2 in electrophilic attacks as a major hydrophilic surface area. Pyz due to a neutral electrostatic potential has no role in electrophilic and nucleophilic attacks (Figure 20), whereas with NIQ, the O atom of >C�O is more reactive than the other O atoms of NO 2 for electrophilic sites. Reactive behavior and sites of SIQPs and NIQ are evaluated by DFT 38 at the B3LYP/6-311++G (df, pd) level.

CONCLUSION
A complete photocatalysis of dyes with SIQP photocatalysts is achieved in mixed solvent under SL. SIQPI, II, and III with NaCl reduced the QHIn in 120, 28 The dye photoreduction depends on pH, T, and nature of electrolyte. The PCR activities of SIQPs are being pursued to focus their scope for structural change of biomolecules of the biological systems. This approach could be applied for photocatalysis, electrocatalysis, and thermocatalysis or in combination. Eventually, the photomechanism could pave a way for a sustainable photodegradation of waste biomass.