10.1039/b910641c
Hydrothermal chemistry of vanadium oxides with aromatic di- and tri-phosphonates in the presence of secondary metal copper(II) cationic complex subunits
 All chemicals were used as obtained without further purification: vanadium(V) oxide, copper(II) acetate hydrate, copper(II) nitrate hydrate, 2,2'-dipyridine, 2,2'-dipyridylamine, 1,10-phenanthroline, 2,2':6,2''-terpyridine, and hydrofluoric acid (48 to 51%) were purchased from Aldrich. The phosphonate ligands 1,4-phenyldiphosphonic acid, 1,3-phenyldiphosphonic acid, and 1,3,5-phenyltriphosphonic acid were prepared according to the literature method.57 The copper mononucleating ligand 2-pyridylcarboxylic acid was prepared by refluxing 2-cyanopyridine in concentrated HCl overnight, and subsequent removal of excess liquid. All syntheses were carried out in 23mL poly(tetrafluoroethylene) lined stainless steel containers under autogenous pressure. The reactants were stirred briefly and initial pH was measured before heating. Water was distilled above 3.0 M Ω in-house using a Barnstead Model 525 Biopure Distilled Water Center. The reactions initial and final pH was measured using Hydrion pH sticks. 
A mixture of V2O5 (0.078g, 0.429mmol), cupric acetate hydrate (0.212g, 1.17mmol), 1,10-phenanthroline (0.087 g, 0.483 mmol), 1,3-phenyldiphosphonic acid (0.048 g, 0.202 mmol), and H2O (5.00 mL, 277.47 mmol) in the mole ratio 2.12:5.79:2.39:1.00:1374 was stirred briefly before heating to 150 degC for 72 h. Initial and final pH values of 3.0 and 3.0, respectively, were recorded. Found: C, 39.6; H, 2.33; N, 6.03. 
A solution of V2O5 (0.078 g, 0.429 mmol), cupric nitrate hydrate (0.201 g, 0.864 mmol), 1,10-phenanthroline (0.083 g, 0.461 mmol), 1,3-phenyldiphosphonic acid (0.051g, 0.214mmol), H2O (5.00mL, 277.47mmol), and HF (0.400mL, 11.60mmol) in the mole ratio 2.00:4.04:2.15:1.00:1297:54.21 was heated at 150 degC for 72h (initial and final pH:1.0 and 1.0, respectively). Blue plates of 2 suitable for X-ray diffraction were isolated in 65% yield. 
The solution of V2O5 (0.077g, 0.423mmol), cupric acetate hydrate (0.210 g, 1.16 mmol), 2,2':6,2'' terpyridine (0.103 g, 0.442 mmol), 1,3-phenyldiphosphonic acid (0.051 g, 0.214 mmol), H2O (5.00 mL, 277.47 mmol), and acetic acid (0.100 mL, 1.74 mmol) in the mole ratio 1.98:5.42:2.07:1.00:1297:8.13 was heated to 135 degC for 60 h and provided green blocks of 3 in 30% yield (initial pH: 3.0, final pH: 3.0). 
The reaction of V2O5 (0.077 g, 0.423 mmol), cupric acetate hydrate (0.207 g, 1.14 mmol), 2,2'dipyridylamine (0.083 g, 0.485 mmol), 1,3-phenyldiphosphonic acid (0.049 g, 0.206 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.100 mL, 2.90 mmol) in the mole ratio 2.05:5.53:2.35:1.00:1347:14.08 at 135 degC for 48 h produced green plates of 4 in 40% yield (initial pH: 2.0, final pH: 1.0). 
The reactants V2O5 (0.077 g, 0.423 mmol), cupric acetate hydrate (0.206 g, 1.13 mmol), 2,2'dipyridylamine (0.084 g, 0.491 mmol), 1,3-phenyldiphosphonic acid (0.052 g, 0.218 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.200 mL, 5.80 mmol) in the mole ratio 1.94:5.18:2.25:1.00:1273:26.61 were stirred briefly before heating to 135 degC for 48h. Dark green plates of 5 suitable for X-ray diffraction were isolated in 85% yield. 
A reaction of V2O5 (0.080 g, 0.440 mmol), cupric acetate hydrate (0.201 g, 0.864 mmol), 1,10-phenanthroline (0.083 g, 0.461 mmol), 1,4-phenyldiphosphonic acid (0.051 g, 0.214 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.100 mL, 2.90 mmol) with the mole ratio 2.06:4.14:2.15:1.00:1297:13.55 was stirred briefly before heating to 120 degC for 72h. 
A mixture of V2O5 (0.079 g, 0.434 mmol), cupric acetate hydrate (0.200 g, 0.860 mmol), 1,10-phenanthroline (0.084 g, 0.466 mmol), 1,4-phenyldiphosphonic acid (0.050 g, 0.210 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.400 mL, 11.60 mmol) with the mole ratio 2.07:4.10:2.22:1.00:1321:55.24 was stirred briefly before heating to 120 degC for 72 h (initial and final pH values of 0.5 and 0.5, respectively). Blue plates of 7a were isolated in 65% yield which were suitable for X-ray diffraction. 
A mixture of V2O5 (0.077 g, 0.423 mmol), cupric acetate hydrate (0.203 g, 0.873 mmol), 1,10-phenanthroline (0.084 g, 0.466 mmol), 1,4-phenyldiphosphonic acid (0.049 g, 0.206 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.100 mL, 2.90 mmol) with the mole ratio 2.05:4.24:2.26:1.00:1347:14.08 was stirred briefly before heating to 150 degC for 72h (initial and final pH values of 1.0 and 1.0, respectively). 
A mixture of V2O5 (0.082 g, 0.451 mmol), cupric acetate hydrate (0.201 g, 0.864 mmol), 2-pyridyl carboxylic acid (0.130 g, 1.060 mmol), 1,4-phenyldiphosphonic acid (0.050 g, 0.210 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.200 mL, 5.80 mmol) with the mole ratio 2.15:4.11:5.05:1.00:1321:27.61 was stirred briefly before heating to 120 degC for 72 h. Green plates of 8 were isolated in 35% yield and were suitable for X-ray diffraction. 
A solution of V2O5 (0.078 g, 0.428 mmol), cupric acetate hydrate (0.201 g, 0.864 mmol), 2,2'-dipyridyl (0.065 g, 0.416 mmol), 1,4-phenyldiphosphonic acid (0.047 g, 0.197 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.200 mL, 5.80 mmol) with the mole ratio 2.17:4.39:2.11:1.00:1408:29.44 was stirred briefly before heating to 120 degC for 72 h with an initial and final pH of 1.0,.5. Dark green plates of 9 were isolated in 40% yield which were suitable for X-ray diffraction. for C13 H10 Cu F N2 O5 P V: C, 35.6; H, 2.28; N, 6.38. A reaction of V2O5 (0.079 g, 0.434 mmol), cupric acetate hydrate (0.201 g, 0.864 mmol), 2,2':6,2'' terpyridine (0.100 g, 0.429 mmol), 1,4-phenyldiphosphonic acid (0.049 g, 0.206 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.200 mL, 5.80 mmol) with the mole ratio 2.11:4.19:2.08:1.00:1347:28.16 was stirred briefly before heating to 180 degC for 48 h. Initial and final pH values of 1.0 and 1.0, respectively, were recorded. Blue blocks of 10 were isolated in 65% yield. A mixture of V2O5 (0.077 g, 0.423 mmol), cupric acetate hydrate (0.202 g, 0.868 mmol), 2,2'-dipyridylamine (0.075 g, 0.438 mmol), 1,4-phenyldiphosphonic acid (0.049 g, 0.206 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.100 mL, 2.90 mmol) with the mole ratio 2.05:4.21:2.13:1.00:1347:14.08 was stirred briefly before heating to 150 degC for 96 h. Dark green blocks of 11 were isolated in 10% yield and were suitable for X-ray diffraction. Found: C, 34.8; H, 2.25; N, 8.88. 
Synthesis of [Cu(bpy)VO2 {(HO3P)3C6H3}]*1.5H2O (12*1.5H2O). 
The solution of V2O5 (0.076 g, 0.42 mmol), cupric nitrate hydrate (0.202 g, 0.87 mmol), 2,2'-dipyridyl (0.065 g, 0.42 mmol), 1,3,5-phenyltriphosphonic acid (0.069 g, 0.22 mmol), H2O (5.00 mL, 277.47 mmol) and HF (400 uL, 11.60 mmol) in the mole ratio 1.92:4.00:1.92:1.00:1280:53.46 was heated to 150 degC for 72 h and provided blue blocks of 12 in 60% yield (initial pH:1.0, final pH:1.0). 
The reaction of V2O5 (0.078 g, 0.43 mmol), cupric nitrate hydrate (0.205 g, 0.88 mmol), 2,2'-dipyridyl (0.066 g, 0.42 mmol), 1,3,5-phenyltriphosphonic acid (0.06 7g, 0.21 mmol), H2O (5.00 mL, 277.47 mmol) and HF (100 uL, 2.90 mmol) in the mole ratio 2.03:4.18:2.00:1.00:1315:13.74 at 180 degC for 72 h produced green needles of 13 in 40% yield (initial pH:1.0, final pH:1.0). 
The reactants V2O5 (0.080 g, 0.44 mmol), cupric nitrate hydrate (0.205 g, 0.88 mmol), 1,10-phenanthroline (0.083 g, 0.46 mmol), 1,3,5-phenyltriphosphonic acid (0.069 g, 0.22 mmol), H2O (5.00 mL, 277.47 mmol) and HF (100 uL, 2.90 mmol) in the mole ratio 2.03:4.06:2.12:1.00:1279:11.34 were stirred briefly before heating to 180 degC for 72 h. Green needles of 14 suitable for X-ray diffraction were isolated in 15% yield. A mixture of V2O5 (0.078 g, 0.429 mmol), cupric nitrate hydrate (0.203 g, 0.873 mmol), 2-pyridyl carboxylic acid (0.060 g, 0.487 mmol), 1,3-phenyldiphosphonic acid (0.048 g, 0.202 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.200 mL, 5.80 mmol) in the mole ratio 2.12:4.32:2.41:1.00:1374:28.71 was heated to 135 degC for 48 h. Initial and final pH values of 1.0 and 1.0, respectively, were recorded. Found: C, 38.5; H, 3.01; N, 4.72. A mixture of V2O5 (0.079 g, 0.434 mmol), cupric acetate hydrate (0.204 g, 0.877 mmol), 2-pyridyl carboxylic acid (0.128 g, 1.039 mmol), 1,4-phenyldiphosphonic acid (0.049 g, 0.206 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.400 mL, 11.60 mmol) with the mole ratio 2.11:4.26:5.04:1.00:1347:56.31. The reaction was stirred briefly before heating to 120 degC for 72 h with an initial and final pH of 1.0, 1.0. 
A mixture of V2O5 (0.078 g, 0.43 mmol), cupric nitrate hydrate (0.200 g, 0.86 mmol), 2,2'-dipyridyl (0.066 g, 0.42 mmol), 1,3,5-phenyltriphosphonic acid (0.068 g, 0.21 mmol), H2O (5.00 mL, 277.47 mmol) and HF (800 uL, 23.20 mmol) in the mole ratio 2.00:4.02:1.98:1.00:1297:108.41 was heated to 150 degC for 72 h. Initial and final pH values of 1.0 and 1.0, respectively, were recorded. Blue blocks of 17 suitable for X-ray diffraction were isolated in 80% yield. 
The solution of V2O5 (0.079 g, 0.43 mmol), cupric nitrate hydrate (0.203 g, 0.87 mmol), 2,2'-dipyridyl (0.067 g, 0.43 mmol), 1,3,5-phenyltriphosphonic acid (0.067 g, 0.21 mmol), H2O (5.00 mL, 277.47 mmol) and HF (1000 uL, 29.00 mmol) in the mole ratio 2.06:4.14:2.03:1.00:1315:137.44 was heated to 120 degC for 72 h to give blue blocks of 18 in 70% yield (initial pH:1.0, final pH:1.0). 
The reaction of V2O5 (0.079 g, 0.43 mmol), cupric nitrate hydrate (0.210 g, 0.90 mmol), 1,10-phenanthroline (0.086 g, 0.48 mmol), 1,3,5-phenyltriphosphonic acid (0.067 g, 0.21 mmol), H2O (5.00 mL, 277.47 mmol) and HF (800 uL, 23.20 mmol) in the mole ratio 2.06:4.28:2.26:1.00:1315:109.95 at 180 degC for 72 h produced blue blocks of 19 in 50% yield (initial pH:1.0, final pH:1.0). 
Synthesis of [Cu(bpa){H2O3PC6H3(PO3H)2}]*H2O (20*H2O). 
The reactants V2O5 (0.081 g, 0.45 mmol), cupric acetate hydrate (0.211 g, 1.16 mmol), 2,2'-bipyridyl amine (0.083 g, 0.49 mmol), 1,3,5-phenyltriphosphonic acid (0.086 g, 0.27 mmol), H2O (5.00 mL, 277.47 mmol) and HF (800 uL, 23.20 mmol) in the mole ratio 1.65:4.30:1.80:1.00:1028:85.93 were stirred briefly before heating to 135 degC for 72 h.
hydrofluoric acid
48 to 51%
%
stainless steel containers
poly(tetrafluoroethylene)
23mL
mL
Water
distilled
3.0 M
M
V2O5
mixture
0.078g
g
V2O5
mixture
0.429mmol
mmol
cupric acetate hydrate
mixture
0.212g
g
cupric acetate hydrate
mixture
1.17mmol
mmol
1,10-phenanthroline
mixture
0.087 g
g
1,10-phenanthroline
mixture
0.483 mmol
mmol
1,3-phenyldiphosphonic acid
mixture
0.048 g
g
1,3-phenyldiphosphonic acid
mixture
0.202 mmol
mmol
H2O
mixture
5.00 mL
mL
H2O
mixture
277.47 mmol
mmol
mixture of V2O5 (0.078g, 0.429mmol), cupric acetate hydrate (0.212g, 1.17mmol), 1,10-phenanthroline (0.087 g, 0.483 mmol), 1,3-phenyldiphosphonic acid (0.048 g, 0.202 mmol), and H2O (5.00 mL, 277.47 mmol)
mole ratio
2.12:5.79:2.39:1.00:1374
mixture
heating
150 degC
degC
mixture
heating
72 h
h
mixture
pH values
3.0
mixture
pH values
3.0
C
39.6
H
2.33
N
6.03
V2O5
solution
0.078 g
g
V2O5
solution
0.429 mmol
mmol
cupric nitrate hydrate
solution
0.201 g
g
cupric nitrate hydrate
solution
0.864 mmol
mmol
1,10-phenanthroline
solution
0.083 g
g
1,10-phenanthroline
solution
0.461 mmol
mmol
1,3-phenyldiphosphonic acid
solution
0.214mmol
mmol
H2O
solution
5.00mL
mL
H2O
solution
277.47mmol
mmol
HF
solution
0.400mL
mL
HF
solution
11.60mmol
mmol
solution of V2O5 (0.078 g, 0.429 mmol), cupric nitrate hydrate (0.201 g, 0.864 mmol), 1,10-phenanthroline (0.083 g, 0.461 mmol), 1,3-phenyldiphosphonic acid (0.051g, 0.214mmol), H2O (5.00mL, 277.47mmol), and HF (0.400mL, 11.60mmol)
mole ratio
2.00:4.04:2.15:1.00:1297:54.21
solution
heated
150 degC
degC
solution
heated
72h
h
solution
pH
1.0
solution
pH
1.0
1,3-phenyldiphosphonic acid
0.051g
g
Blue plates
yield
65%
%
solution
V2O5
0.077g
g
solution
V2O5
0.423mmol
mmol
solution
cupric acetate hydrate
0.210 g
g
solution
cupric acetate hydrate
1.16 mmol
mmol
solution
terpyridine
0.103 g
g
solution
terpyridine
0.442 mmol
mmol
solution
1,3-phenyldiphosphonic acid
0.051 g
g
solution
1,3-phenyldiphosphonic acid
0.214 mmol
mmol
solution
H2O
5.00 mL
mL
solution
H2O
277.47 mmol
mmol
solution
acetic acid
0.100 mL
mL
solution
acetic acid
1.74 mmol
mmol
V2O5 (0.077g, 0.423mmol), cupric acetate hydrate (0.210 g, 1.16 mmol), 2,2':6,2'' terpyridine (0.103 g, 0.442 mmol), 1,3-phenyldiphosphonic acid (0.051 g, 0.214 mmol), H2O (5.00 mL, 277.47 mmol), and acetic acid
mole ratio
1.98:5.42:2.07:1.00:1297:8.13
solution
heated
135 degC
degC
solution
heated
60 h
h
green blocks
yield
30%
%
solution
pH
3.0
solution
pH
3.0
green blocks
3
reaction
V2O5
0.077 g
g
reaction
V2O5
0.423 mmol
mmol
reaction
cupric acetate hydrate
0.207 g
g
reaction
cupric acetate hydrate
1.14 mmol
mmol
reaction
2,2'dipyridylamine
0.083 g
g
reaction
2,2'dipyridylamine
0.485 mmol
mmol
reaction
1,3-phenyldiphosphonic acid
0.049 g
g
reaction
1,3-phenyldiphosphonic acid
0.206 mmol
mmol
reaction
H2O
5.00 mL
mL
reaction
H2O
277.47 mmol
mmol
reaction
HF
0.100 mL
mL
reaction
HF
2.90 mmol
mmol
V2O5 (0.077 g, 0.423 mmol), cupric acetate hydrate (0.207 g, 1.14 mmol), 2,2'dipyridylamine (0.083 g, 0.485 mmol), 1,3-phenyldiphosphonic acid (0.049 g, 0.206 mmol), H2O (5.00 mL, 277.47 mmol), and HF
mole ratio
2.05:5.53:2.35:1.00:1347:14.08
reaction
135 degC
degC
reaction
48 h
h
produced green plates
4
green plates
yield
40%
%
reaction
pH
2.0
reaction
pH
1.0
V2O5
stirred
0.077 g
g
H2O
stirred
277.47 mmol
mmol
HF
stirred
0.200 mL
mL
HF
stirred
5.80 mmol
mmol
V2O5 (0.077 g, 0.423 mmol), cupric acetate hydrate (0.206 g, 1.13 mmol), 2,2'dipyridylamine (0.084 g, 0.491 mmol), 1,3-phenyldiphosphonic acid (0.052 g, 0.218 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.200 mL, 5.80 mmol)
mole ratio
1.94:5.18:2.25:1.00:1273:26.61
reactants V2O5 (0.077 g, 0.423 mmol), cupric acetate hydrate (0.206 g, 1.13 mmol), 2,2'dipyridylamine (0.084 g, 0.491 mmol), 1,3-phenyldiphosphonic acid (0.052 g, 0.218 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.200 mL, 5.80 mmol)
heating
135 degC
degC
reactants V2O5 (0.077 g, 0.423 mmol), cupric acetate hydrate (0.206 g, 1.13 mmol), 2,2'dipyridylamine (0.084 g, 0.491 mmol), 1,3-phenyldiphosphonic acid (0.052 g, 0.218 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.200 mL, 5.80 mmol)
heating
48h
h
cupric acetate hydrate
stirred
0.206 g
g
2,2'dipyridylamine
stirred
0.084 g
g
2,2'dipyridylamine
stirred
0.491 mmol
mmol
1,3-phenyldiphosphonic acid
stirred
0.052 g
g
1,3-phenyldiphosphonic acid
stirred
0.218 mmol
mmol
H2O
stirred
5.00 mL
mL
V2O5
stirred
0.423 mmol
mmol
cupric acetate hydrate
stirred
1.13 mmol
mmol
Dark green plates
5
Dark green plates
yield
85%
%
V2O5 (0.080 g, 0.440 mmol), cupric acetate hydrate (0.201 g, 0.864 mmol), 1,10-phenanthroline (0.083 g, 0.461 mmol), 1,4-phenyldiphosphonic acid (0.051 g, 0.214 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.100 mL, 2.90 mmol)
mole ratio
2.06:4.14:2.15:1.00:1297:13.55
V2O5 (0.080 g, 0.440 mmol), cupric acetate hydrate (0.201 g, 0.864 mmol), 1,10-phenanthroline (0.083 g, 0.461 mmol), 1,4-phenyldiphosphonic acid (0.051 g, 0.214 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.100 mL, 2.90 mmol)
heating
120 degC
degC
V2O5 (0.080 g, 0.440 mmol), cupric acetate hydrate (0.201 g, 0.864 mmol), 1,10-phenanthroline (0.083 g, 0.461 mmol), 1,4-phenyldiphosphonic acid (0.051 g, 0.214 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.100 mL, 2.90 mmol)
heating
72h
h
V2O5
stirred
0.080 g
g
V2O5
stirred
0.440 mmol
mmol
cupric acetate hydrate
stirred
0.201 g
g
cupric acetate hydrate
stirred
0.864 mmol
mmol
1,10-phenanthroline
stirred
0.083 g
g
1,10-phenanthroline
stirred
0.461 mmol
mmol
1,4-phenyldiphosphonic acid
stirred
0.051 g
g
1,4-phenyldiphosphonic acid
stirred
0.214 mmol
mmol
H2O
stirred
5.00 mL
mL
H2O
stirred
277.47 mmol
mmol
HF
stirred
0.100 mL
mL
HF
stirred
2.90 mmol
mmol
V2O5
0.079 g
g
V2O5
mixture
0.434 mmol
mmol
cupric acetate hydrate
mixture
0.200 g
g
cupric acetate hydrate
mixture
0.860 mmol
mmol
1,10-phenanthroline
mixture
0.084 g
g
1,10-phenanthroline
mixture
0.466 mmol
mmol
1,4-phenyldiphosphonic acid
mixture
0.050 g
g
1,4-phenyldiphosphonic acid
mixture
0.210 mmol
mmol
H2O
mixture
5.00 mL
mL
H2O
mixture
277.47 mmol
mmol
HF
mixture
0.400 mL
mL
HF
mixture
11.60 mmol
mmol
mixture of V2O5 (0.079 g, 0.434 mmol), cupric acetate hydrate (0.200 g, 0.860 mmol), 1,10-phenanthroline (0.084 g, 0.466 mmol), 1,4-phenyldiphosphonic acid (0.050 g, 0.210 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.400 mL, 11.60 mmol)
mole ratio
2.07:4.10:2.22:1.00:1321:55.24
mixture
heating
120 degC
degC
mixture
heating
72 h
h
mixture
pH values
0.5
mixture
pH values
0.5
Blue plates
isolated
7
Blue plates
yield
65%
%
mixture
V2O5
0.077 g
g
mixture
V2O5
0.423 mmol
mmol
mixture
cupric acetate hydrate
0.203 g
g
mixture
cupric acetate hydrate
0.873 mmol
mmol
mixture
1,10-phenanthroline
0.084 g
g
mixture
1,10-phenanthroline
0.466 mmol
mmol
mixture
1,4-phenyldiphosphonic acid
0.049 g
g
mixture
1,4-phenyldiphosphonic acid
0.206 mmol
mmol
mixture
H2O
5.00 mL
mL
mixture
H2O
277.47 mmol
mmol
mixture
HF
0.100 mL
mL
mixture
HF
2.90 mmol
mmol
V2O5 (0.077 g, 0.423 mmol), cupric acetate hydrate (0.203 g, 0.873 mmol), 1,10-phenanthroline (0.084 g, 0.466 mmol), 1,4-phenyldiphosphonic acid (0.049 g, 0.206 mmol), H2O (5.00 mL, 277.47 mmol), and HF
mole ratio
2.05:4.24:2.26:1.00:1347:14.08
mixture
heating
150 degC
degC
mixture
heating
72h
h
mixture
pH
1.0
mixture
pH
1.0
mixture
V2O5
0.082 g
g
mixture
V2O5
0.451 mmol
mmol
mixture
cupric acetate hydrate
0.201 g
g
mixture
cupric acetate hydrate
0.864 mmol
mmol
mixture
2-pyridyl carboxylic acid
0.130 g
g
mixture
2-pyridyl carboxylic acid
1.060 mmol
mmol
mixture
1,4-phenyldiphosphonic acid
0.050 g
g
mixture
1,4-phenyldiphosphonic acid
0.210 mmol
mmol
mixture
H2O
5.00 mL
mL
mixture
H2O
277.47 mmol
mmol
mixture
HF
0.200 mL
mL
mixture
HF
5.80 mmol
mmol
f V2O5 (0.082 g, 0.451 mmol), cupric acetate hydrate (0.201 g, 0.864 mmol), 2-pyridyl carboxylic acid (0.130 g, 1.060 mmol), 1,4-phenyldiphosphonic acid (0.050 g, 0.210 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.200 mL, 5.80 mmol)
mole ratio
2.15:4.11:5.05:1.00:1321:27.61
mixture
heating
120 degC
degC
mixture
heating
72 h
h
Green plates
isolated
8
Green plates
yield
35%
%
solution
V2O5
0.078 g
g
solution
V2O5
0.428 mmol
mmol
solution
cupric acetate hydrate
0.201 g
g
solution
cupric acetate hydrate
0.864 mmol
mmol
solution
2,2'-dipyridyl
0.065 g
g
solution
2,2'-dipyridyl
0.416 mmol
mmol
solution
1,4-phenyldiphosphonic acid
0.047 g
g
solution
1,4-phenyldiphosphonic acid
0.197 mmol
mmol
solution
H2O
5.00 mL
mL
solution
H2O
277.47 mmol
mmol
solution
HF
0.200 mL
mL
solution
HF
5.80 mmol
mmol
V2O5 (0.078 g, 0.428 mmol), cupric acetate hydrate (0.201 g, 0.864 mmol), 2,2'-dipyridyl (0.065 g, 0.416 mmol), 1,4-phenyldiphosphonic acid (0.047 g, 0.197 mmol), H2O (5.00 mL, 277.47 mmol), and HF
mole ratio
2.17:4.39:2.11:1.00:1408:29.44
solution
heating
120 degC
degC
solution
heating
72 h
h
solution
pH
1.0
solution
pH
.5
Dark green plates
isolated
9
Dark green plates
yield
40%
%
O
5
N
2
H
10
C
13
C13 H10 Cu F N2 O5 P V
C
35.6
C13 H10 Cu F N2 O5 P V
H
2.28
C13 H10 Cu F N2 O5 P V
N
6.38
V2O5 (0.079 g, 0.434 mmol), cupric acetate hydrate (0.201 g, 0.864 mmol), 2,2':6,2'' terpyridine (0.100 g, 0.429 mmol), 1,4-phenyldiphosphonic acid (0.049 g, 0.206 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.200 mL, 5.80 mmol)
mole ratio
2.11:4.19:2.08:1.00:1347:28.16
V2O5
stirred
0.079 g
g
V2O5
stirred
0.434 mmol
mmol
cupric acetate hydrate
stirred
0.201 g
g
cupric acetate hydrate
stirred
0.864 mmol
mmol
2,2':6,2'' terpyridine
stirred
0.100 g
g
2,2':6,2'' terpyridine
stirred
0.429 mmol
mmol
1,4-phenyldiphosphonic acid
stirred
0.049 g
g
1,4-phenyldiphosphonic acid
stirred
0.206 mmol
mmol
H2O
stirred
5.00 mL
mL
H2O
stirred
277.47 mmol
mmol
HF
stirred
0.200 mL
mL
HF
stirred
5.80 mmol
mmol
reaction
heating
180 degC
degC
reaction
heating
48 h
h
reaction
pH values
1.0
reaction
pH values
1.0
Blue blocks
yield
%
Blue blocks
isolated
10
mixture
V2O5
0.077 g
g
mixture
V2O5
0.423 mmol
mmol
mixture
cupric acetate hydrate
0.202 g
g
mixture
cupric acetate hydrate
0.868 mmol
mmol
mixture
2,2'-dipyridylamine
0.075 g
g
mixture
2,2'-dipyridylamine
0.438 mmol
mmol
mixture
1,4-phenyldiphosphonic acid
0.049 g
g
mixture
1,4-phenyldiphosphonic acid
0.206 mmol
mmol
mixture
H2O
5.00 mL
mL
mixture
H2O
277.47 mmol
mmol
mixture
HF
0.100 mL
mL
mixture
HF
2.90 mmol
mmol
V2O5 (0.077 g, 0.423 mmol), cupric acetate hydrate (0.202 g, 0.868 mmol), 2,2'-dipyridylamine (0.075 g, 0.438 mmol), 1,4-phenyldiphosphonic acid (0.049 g, 0.206 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.100 mL, 2.90 mmol)
mole ratio
2.05:4.21:2.13:1.00:1347:14.08
mixture
heating
150 degC
degC
mixture
heating
96 h
h
Dark green blocks
isolated
11
Dark green blocks
yield
10%
%
C
34.8
H
2.25
N
8.88
solution
V2O5
0.076 g
g
solution
V2O5
0.42 mmol
mmol
solution
cupric nitrate hydrate
0.202 g
g
solution
cupric nitrate hydrate
0.87 mmol
mmol
solution
2,2'-dipyridyl
0.065 g
g
solution
2,2'-dipyridyl
0.42 mmol
mmol
solution
1,3,5-phenyltriphosphonic acid
0.069 g
g
solution
1,3,5-phenyltriphosphonic acid
0.22 mmol
mmol
solution
H2O
5.00 mL
mL
solution
H2O
277.47 mmol
mmol
solution
HF
400 uL
uL
solution
HF
11.60 mmol
mmol
V2O5 (0.076 g, 0.42 mmol), cupric nitrate hydrate (0.202 g, 0.87 mmol), 2,2'-dipyridyl (0.065 g, 0.42 mmol), 1,3,5-phenyltriphosphonic acid (0.069 g, 0.22 mmol), H2O (5.00 mL, 277.47 mmol) and HF (400 uL, 11.60 mmol)
mole ratio
1.92:4.00:1.92:1.00:1280:53.46
solution
heated
150 degC
degC
solution
heated
72 h
h
solution
blue blocks
12
solution
yield
60%
%
solution
initial pH
1.0
solution
final pH
1.0
reaction
V2O5
0.078 g
g
reaction
V2O5
0.43 mmol
mmol
reaction
cupric nitrate hydrate
0.205 g
g
reaction
cupric nitrate hydrate
0.88 mmol
mmol
reaction
2,2'-dipyridyl
0.066 g
g
reaction
2,2'-dipyridyl
0.42 mmol
mmol
reaction
1,3,5-phenyltriphosphonic acid
0.06 7g
g
reaction
1,3,5-phenyltriphosphonic acid
0.21 mmol
mmol
reaction
H2O
5.00 mL
mL
reaction
H2O
277.47 mmol
mmol
reaction
HF
100 uL
uL
reaction
HF
2.90 mmol
mmol
V2O5 (0.078 g, 0.43 mmol), cupric nitrate hydrate (0.205 g, 0.88 mmol), 2,2'-dipyridyl (0.066 g, 0.42 mmol), 1,3,5-phenyltriphosphonic acid (0.06 7g, 0.21 mmol), H2O (5.00 mL, 277.47 mmol) and HF
mole ratio
2.03:4.18:2.00:1.00:1315:13.74
reaction
180 degC
degC
reaction
72 h
h
green needles
13
green needles
yield
40%
%
reaction
pH
1.0
reaction
pH
1.0
V2O5
reactants
0.44 mmol), cupric nitrate hydrate (0.205 g, 0.88 mmol), 1,10-phenanthroline (0.083 g, 0.46 mmol
mmol
H2O
reactants
5.00 mL
mL
1,3,5-phenyltriphosphonic acid
reactants
0.22 mmol
mmol
reactants
heating
72 h
h
reactants V2O5 (0.080 g, 0.44 mmol), cupric nitrate hydrate (0.205 g, 0.88 mmol), 1,10-phenanthroline (0.083 g, 0.46 mmol), 1,3,5-phenyltriphosphonic acid (0.069 g, 0.22 mmol), H2O (5.00 mL, 277.47 mmol) and HF (100 uL, 2.90 mmol)
mole ratio
2.03:4.06:2.12:1.00:1279:11.34
V2O5
reactants
0.080 g
g
1,10-phenanthroline
reactants
0.083 g
g
cupric nitrate hydrate
reactants
0.88 mmol
mmol
H2O
reactants
277.47 mmol
mmol
HF
reactants
2.90 mmol
mmol
cupric nitrate hydrate
reactants
0.205 g
g
HF
reactants
100 uL
uL
1,3,5-phenyltriphosphonic acid
reactants
0.069 g
g
reactants
heating
180 degC
degC
Green needles
isolated
14
Green needles
yield
15%
%
V2O5
mixture
0.078 g
g
V2O5
mixture
0.429 mmol
mmol
, cupric nitrate hydrate
mixture
0.203 g
g
cupric nitrate hydrate
mixture
0.873 mmol
mmol
2-pyridyl carboxylic acid
mixture
0.060 g
g
2-pyridyl carboxylic acid
mixture
0.487 mmol
mmol
1,3-phenyldiphosphonic acid
mixture
0.048 g
g
1,3-phenyldiphosphonic acid
mixture
0.202 mmol
mmol
H2O
mixture
5.00 mL
mL
H2O
mixture
277.47 mmol
mmol
HF
mixture
0.200 mL
mL
HF
mixture
5.80 mmol
mmol
mixture of V2O5 (0.078 g, 0.429 mmol), cupric nitrate hydrate (0.203 g, 0.873 mmol), 2-pyridyl carboxylic acid (0.060 g, 0.487 mmol), 1,3-phenyldiphosphonic acid (0.048 g, 0.202 mmol), H2O (5.00 mL, 277.47 mmol), and HF (0.200 mL, 5.80 mmol)
mole ratio
2.12:4.32:2.41:1.00:1374:28.71
mixture
heated
135 degC
degC
mixture
heated
48 h
h
mixture
pH values
1.0
mixture
pH values
1.0
C
38.5
H
3.01
N
4.72
mixture
V2O5
0.079 g
g
mixture
V2O5
0.434 mmol
mmol
mixture
cupric acetate hydrate
0.204 g
g
mixture
cupric acetate hydrate
0.877 mmol
mmol
mixture
2-pyridyl carboxylic acid
0.128 g
g
mixture
2-pyridyl carboxylic acid
1.039 mmol
mmol
mixture
1,4-phenyldiphosphonic acid
0.049 g
g
mixture
1,4-phenyldiphosphonic acid
0.206 mmol
mmol
mixture
H2O
5.00 mL
mL
mixture
H2O
277.47 mmol
mmol
mixture
HF
0.400 mL
mL
mixture
HF
11.60 mmol
mmol
V2O5 (0.079 g, 0.434 mmol), cupric acetate hydrate (0.204 g, 0.877 mmol), 2-pyridyl carboxylic acid (0.128 g, 1.039 mmol), 1,4-phenyldiphosphonic acid (0.049 g, 0.206 mmol), H2O (5.00 mL, 277.47 mmol), and HF
mole ratio
2.11:4.26:5.04:1.00:1347:56.31
reaction
heating
120 degC
degC
reaction
heating
72 h
h
reaction
pH
1.0
reaction
pH
1.0
V2O5
mixture
0.078 g
g
V2O5
mixture
0.43 mmol
mmol
cupric nitrate hydrate
mixture
0.200 g
g
cupric nitrate hydrate
mixture
0.86 mmol
mmol
2,2'-dipyridyl
mixture
0.066 g
g
2,2'-dipyridyl
mixture
0.42 mmol
mmol
1,3,5-phenyltriphosphonic acid
mixture
0.068 g
g
1,3,5-phenyltriphosphonic acid
mixture
0.21 mmol
mmol
H2O
mixture
5.00 mL
mL
H2O
mixture
277.47 mmol
mmol
HF
mixture
800 uL
uL
HF
mixture
23.20 mmol
mmol
mixture of V2O5 (0.078 g, 0.43 mmol), cupric nitrate hydrate (0.200 g, 0.86 mmol), 2,2'-dipyridyl (0.066 g, 0.42 mmol), 1,3,5-phenyltriphosphonic acid (0.068 g, 0.21 mmol), H2O (5.00 mL, 277.47 mmol) and HF (800 uL, 23.20 mmol)
mole ratio
2.00:4.02:1.98:1.00:1297:108.41
mixture
heated
150 degC
degC
mixture
heated
72 h
h
mixture
pH values
1.0
mixture
pH values
1.0
Blue blocks
isolated
17
Blue blocks
yield
80%
%
solution
V2O5
0.079 g
g
solution
V2O5
0.43 mmol
mmol
solution
cupric nitrate hydrate
0.203 g
g
solution
cupric nitrate hydrate
0.87 mmol
mmol
solution
2,2'-dipyridyl
0.067 g
g
solution
2,2'-dipyridyl
0.43 mmol
mmol
solution
1,3,5-phenyltriphosphonic acid
0.067 g
g
solution
1,3,5-phenyltriphosphonic acid
0.21 mmol
mmol
solution
H2O
5.00 mL
mL
solution
H2O
277.47 mmol
mmol
solution
HF
1000 uL
uL
solution
HF
29.00 mmol
mmol
V2O5 (0.079 g, 0.43 mmol), cupric nitrate hydrate (0.203 g, 0.87 mmol), 2,2'-dipyridyl (0.067 g, 0.43 mmol), 1,3,5-phenyltriphosphonic acid (0.067 g, 0.21 mmol), H2O (5.00 mL, 277.47 mmol) and HF
mole ratio
2.06:4.14:2.03:1.00:1315:137.44
solution
heated
120 degC
degC
solution
heated
72 h
h
blue blocks
18
blue blocks
yield
70%
%
solution
pH
1.0
solution
pH
1.0
V2O5
reaction
0.079 g
g
V2O5
reaction
0.43 mmol
mmol
cupric nitrate hydrate
reaction
0.210 g
g
cupric nitrate hydrate
reaction
0.90 mmol
mmol
1,10-phenanthroline
reaction
0.086 g
g
1,10-phenanthroline
reaction
0.48 mmol
mmol
1,3,5-phenyltriphosphonic acid
reaction
0.067 g
g
1,3,5-phenyltriphosphonic acid
reaction
0.21 mmol
mmol
H2O
reaction
5.00 mL
mL
H2O
reaction
277.47 mmol
mmol
HF
reaction
800 uL
uL
HF
reaction
23.20 mmol
mmol
reaction of V2O5 (0.079 g, 0.43 mmol), cupric nitrate hydrate (0.210 g, 0.90 mmol), 1,10-phenanthroline (0.086 g, 0.48 mmol), 1,3,5-phenyltriphosphonic acid (0.067 g, 0.21 mmol), H2O (5.00 mL, 277.47 mmol) and HF (800 uL, 23.20 mmol)
mole ratio
2.06:4.28:2.26:1.00:1315:109.95
V2O5 (0.079 g, 0.43 mmol), cupric nitrate hydrate (0.210 g, 0.90 mmol), 1,10-phenanthroline (0.086 g, 0.48 mmol), 1,3,5-phenyltriphosphonic acid (0.067 g, 0.21 mmol), H2O (5.00 mL, 277.47 mmol) and HF (800 uL, 23.20 mmol)
reaction
180 degC
degC
V2O5 (0.079 g, 0.43 mmol), cupric nitrate hydrate (0.210 g, 0.90 mmol), 1,10-phenanthroline (0.086 g, 0.48 mmol), 1,3,5-phenyltriphosphonic acid (0.067 g, 0.21 mmol), H2O (5.00 mL, 277.47 mmol) and HF (800 uL, 23.20 mmol)
reaction
72 h
h
reaction
initial pH
1.0
reaction
final pH
1.0
blue blocks
19
blue blocks
yield
50%
%
V2O5
reactants
0.081 g
g
V2O5
reactants
0.45 mmol
mmol
cupric acetate hydrate
reactants
0.211 g
g
cupric acetate hydrate
reactants
1.16 mmol
mmol
2,2'-bipyridyl amine
reactants
0.083 g
g
2,2'-bipyridyl amine
reactants
0.49 mmol
mmol
1,3,5-phenyltriphosphonic acid
reactants
0.086 g
g
1,3,5-phenyltriphosphonic acid
reactants
0.27 mmol
mmol
H2O
reactants
5.00 mL
mL
H2O
reactants
277.47 mmol
mmol
HF
reactants
800 uL
uL
HF
reactants
23.20 mmol
mmol
reactants V2O5 (0.081 g, 0.45 mmol), cupric acetate hydrate (0.211 g, 1.16 mmol), 2,2'-bipyridyl amine (0.083 g, 0.49 mmol), 1,3,5-phenyltriphosphonic acid (0.086 g, 0.27 mmol), H2O (5.00 mL, 277.47 mmol) and HF (800 uL, 23.20 mmol)
mole ratio
1.65:4.30:1.80:1.00:1028:85.93
reactants
heating
135 degC
degC
reactants
heating
72 h
h