DFT Studies of Dimethylaminophenyl-Substituted Phthalocyanine and Its Silver Complexes †
Abstract
:1. Introduction
2. Results
2.1. Gibbs Energies
2.2. DFT-Optimized Structures
2.3. Electronic Structure Characteristics
2.4. TD-DFT Calculated Electron Transitions
3. Discussion
4. Methods
5. Conclusions
Supplementary Materials
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Compound | q | m | G298 (Hartree) | ΔG298 (kJ/mol) |
---|---|---|---|---|
1[dmaphPcAg]+ | +1 | 1 | −4733.24222 | 453.4 |
3[dmaphPcAg]+ | +1 | 3 | −4733.25119 | 429.9 |
2[dmaphPcAg]0 | 0 | 2 | −4733.41492 | 0.0 |
4[dmaphPcAg]0 | 0 | 4 | −4733.38011 | 91.4 |
1[dmaphPcAg]− | −1 | 1 | −4733.51744 | −269.2 |
3[dmaphPcAg]− | −1 | 3 | −4733.51527 | −263.5 |
2[dmaphPcAg]2− | −2 | 2 | −4733.59008 | −459.9 |
4[dmaphPcAg]2− | −2 | 4 | −4733.57970 | −432.6 |
1[dmaphPcH2]0 | 0 | 1 | −4587.58495 | 0.0 |
1[dmaphPcH]− | −1 | 1 | −4587.08582 | 1310.5 |
2[dmaphPcH]0 | 0 | 2 | −4586.94941 | 1668.6 |
1[dmaphPc]2− | −2 | 1 | −4586.54403 | 2732.9 |
2[dmaphPc]− | −1 | 2 | −4586.43712 | 3013.6 |
q | +1 | +1 | 0 | 0 | −1 | −1 | −2 | −2 |
m | 1 | 3 | 2 | 4 | 1 | 3 | 2 | 4 |
Bond length (Å) | ||||||||
Ag-Npy | 2.000(4×) | 2.056(4×) | 2.059(4×) | 2.058(2×) 2.062(2×) | 2.067(2×) 2.133(2×) | 2.063(2×) 2.067(2×) | 2.072(4×) | 2.071(4×) |
Ag—plane distance (Å) | ||||||||
Npy plane | 0.001 | 0.019 | 0.007 | 0.000 | 0.005 | 0.000 | 0.000 | 0.000 |
Bond angle (deg) | ||||||||
(Npy-Ag-Npy)adj | 90.0(4×) | 90.0(4×) | 90.0(4×) | 90.0(4×) | 89.9(2×) 90.1(2×) | 90.0(4×) | 90.0(4×) | 90.0(4×) |
(Npy-Ag-Npy)op | 179.9(2×) | 178.9(2×) | 179.7(2×) | 180.0(2×) | 179.2 179.5 | 180.0(2×) | 180.0(2×) | 180.0(2×) |
Bond order | ||||||||
Ag-Npy | 0.448(4×) | 0.377(4×) | 0.379(4×) | 0.379(2×) 0.377(2×) | 0.363(2×) 0.330(2×) | 0.382(2×) 0.381(2×) | 0.383(4×) | 0.384(4×) |
Charge | ||||||||
Ag | 1.023 | 0.857 | 0.843 | 0.833 | 0.713 | 0.814 | 0.787 | 0.785 |
Npy | −0.574(4×) | −0.623(4×) | −0.614(4×) | −0.613(2×) −0.662(2×) | −0.637(2×) −0.614(2×) | −0.603(2×) −0.647(2×) | −0.633(2×) −0.637(2×) | −0.634(4×) |
Nbr | −0.533(4×) | −0.553(4×) | −0.550(4×) | −0.587(4×) | −0.566(4×) | −0.579(4×) | −0.617(4×) | −0.610(4×) |
Cα | 0.497(8×) | 0.528(8×) | 0.485(8×) | 0.484(4×) 0.532(4×) | 0.464(4×) 0.435(4×) | 0.422(4×) 0.476(4×) | 0.422(8×) | 0.418(8×) |
Cβ | −0.083(8×) | −0.092(8×) | −0.085(8×) | −0.101(4×) −0.086(4×) | −0.083(4×) −0.091(4×) | −0.100(4×) −0.081(4×) | −0.101(8×) | −0.101(8×) |
Namin | −0.482(8×) | −0.475(8×) | −0.492(8×) | −0.489(8×) | −0.497(8×) | −0.497(8×) | −0.502(8×) | −0.502(8×) |
Cmet | −0.418(16×) | −0.418(16×) | −0.418(16×) | −0.418(16×) | −0.418(16×) | −0.418(16×) | −0.418(16×) | −0.418(16×) |
d electron population | ||||||||
Ag | 9.23 | 9.43 | 9.43 | 9.44 | 9.58 | 9.44 | 9.45 | 9.45 |
Spin population | ||||||||
Ag | - | 0.426 | 0.422 | 0.426 | - | 0.420 | 0.412 | 0.415 |
Npy | - | 0.119(4×) | 0.148(4×) | 0.080(2×) 0.206(2×) | - | 0.120(2×) 0.234(2×) | 0.259(2×) 0.039(2×) | 0.208(4×) |
Nbr | - | −0.037(4×) | 0.002(4×) | 0.009(4×) | - | 0.054(4×) | −0.001(4×) | 0.115(4×) |
Cα | - | 0.086(8×) | −0.007(8×) | 0.237(4×) 0.100(4×) | - | 0.104(4×) −0.016(4×) | −0.106(4×) 0.096(4×) | 0.079(8×) |
Cβ | - | −0.007(8×) | 0.006(8×) | 0.016(4×) −0.002(4×) | - | 0.037(4×) 0.004(4×) | −0.043(4×) 0.054(4×) | 0.047(8×) |
Namin | - | 0.016(8×) | 0.000(8×) | 0.005(8×) | - | 0.000(8×) | 0.000(8×) | 0.001(4×) |
Cmet | - | −0.001(16×) | 0.000(16×) | −0.000(16×) | - | 0.000(16×) | 0.000(16×) | 0.000(16×) |
Compound | 1[dmaphPcH2]0 | 1[dmaphPcH]− | 2[dmaphPcH]0 | 1[dmaphPc]2− | 2[dmaphPc]− |
---|---|---|---|---|---|
q | 0 | −1 | 0 | −2 | −1 |
m | 1 | 1 | 2 | 1 | 2 |
Bond length (Å) | |||||
H-Npy | 1.017(2×) | 1.028 | 1.029 | - | - |
Bond order | |||||
H-Npy | 0.659(2×) | 0.648 | 0.645 | - | - |
Charge | |||||
Npy | −0.607(2×) −0.656(2×) | −0.577 −0.613 −0.615 −0.611 | −0.579 −0.617(2×) −0.628 | −0.560(4×) | −0.566(4×) |
Nbr | −0.550(4×) | −0.571(2×) −0.565(2×) | −0.566(2×) −0.571(2×) | −0.588(4×) | −0.592(4×) |
Cα | 0.488(4×) 0.475(4×) | 0.461(2×) 0.462(4×) 0.450(2×) | 0.513(2×) 0.519(2×) 0.510(2×) 0.529(2×) | 0.434(8×) | 0.500(8×) |
Cβ | −0.084(4×) −0.090(4×) | −0.087(2×) −0.085(4×) −0.092(2×) | −0.094(2×) −0.089(2×) −0.097(2×) −0.086(2×) | −0.087(8×) | −0.089(8×) |
Namin | −0.490(4×) −0.492(4×) | −0.497(6×) −0.495(2×) | −0.490(2×) −0.488(4×) −0.486(2×) | −0.503(8×) | −0.496(8×) |
Cmet | −0.418(16×) | −0.418(16×) | −0.418(16×) | −0.419(16×) | −0.418(16×) |
Spin | |||||
Npy | - | - | −0.050 −0.042(2×) −0.023 | - | −0.049(4×) |
Nbr | - | - | −0.050(2×) −0.040(2×) | - | −0.054(4×) |
Cα | 0.125(8×) | 0.140(8×) | |||
Cβ | −0.007(8×) | −0.002(8×) | |||
Namin | - | - | 0.004(4×) 0.003(4×) | - | 0.002(8×) |
Cmet | - | - | 0.000(16×) | - | 0.000(16×) |
System | λexp (nm) | λcalc (nm) | Compound |
---|---|---|---|
2[dmaphPcAg]0 | 300 m | 306(0.3) | 4[dmaphPcAg]0 |
305(0.4) | 1[dmaphPcAg]− | ||
350 m | 358(0.7), 359(0.8), 346(0.4), 345(0.5) | 2[dmaphPcAg]0 | |
355(0.7), 350(0.8) | 4[dmaphPcAg]0 | ||
357(0.3), 355(0.5), 353(0.4), 349(0.5), 342(0.4) | 1[dmaphPcAg]− | ||
343(0.8) | 3[dmaphPcAg]− | ||
364(1.4), 358(1.0), 349(0.4), 344(0.3), 341(0.5), 333(0.6) | 1[dmaphPcH2]0 | ||
325(0.9), 327(0.3), 330(0.5) | 1[dmaphPcH]− | ||
334(0.3) | 2[dmaphPc]− | ||
660 sh | 668(1.0) | 1[dmaphPcAg]− | |
676(1.2), 672(1.2) | 1[dmaphPcH]− | ||
660(1.2), 659(1.2) | 1[dmaphPc]2− | ||
700 m | 701(0.4) | 4[dmaphPcAg]0 | |
687(0.7) | 1[dmaphPcAg]− | ||
730 sh | 724(0.8), 723(0.9) | 2[dmaphPcAg]0 | |
724(1.3) | 3[dmaphPcAg]− | ||
715(0.6) | 4[dmaphPcAg]2− | ||
749(1.0), 736(0.8) | 1[dmaphPcH2]0 | ||
722(0.5), 721(0.5) | 2[dmaphPc]− | ||
1[dmaphPcH2]0 | 340 s | 364(1.4), 358(1.0), 349(0.4), 344(0.3), 341(0.5), 333(0.6) | 1[dmaphPcH2]0 |
325(0.9), 327(0.3), 330(0.5) | 1[dmaphPcH]− | ||
334(0.3) | 2[dmaphPc]− | ||
680 sh | 676(1.2), 672(1.2) | 1[dmaphPcH]− | |
660(1.2), 659(1.2) | 1[dmaphPc]2− | ||
740 s | 749(1.0), 736(0.8) | 1[dmaphPcH2]0 | |
722(0.5), 721(0.5) | 2[dmaphPc]− | ||
Irradiated reaction system | 300 s | 306(0.3) | 4[dmaphPcAg]0 |
305(0.4) | 1[dmaphPcAg]− | ||
350 s | 358(0.7), 359(0.8), 346(0.4), 345(0.5) | 2[dmaphPcAg]0 | |
355(0.7), 350(0.8) | 4[dmaphPcAg]0 | ||
357(0.3), 355(0.5), 353(0.4), 349(0.5), 342(0.4) | 1[dmaphPcAg]− | ||
343(0.8) | 3[dmaphPcAg]− | ||
364(1.4), 358(1.0), 349(0.4), 344(0.3), 341(0.5), 333(0.6) | 1[dmaphPcH2]0 | ||
334(0.3) | 2[dmaphPc]− | ||
450 sh | - | - | |
660 sh | 668(1.0) | 1[dmaphPcAg]− | |
676(1.2), 672(1.2) | 1[dmaphPcH]− | ||
660(1.2), 659(1.2) | 1[dmaphPc]2− | ||
700 s | 701(0.4) | 4[dmaphPcAg]0 | |
687(0.7) | 1[dmaphPcAg]− | ||
720 sh | 724(0.8), 723(0.9) | 2[dmaphPcAg]0 | |
724(1.3) | 3[dmaphPcAg]− | ||
715(0.6) | 4[dmaphPcAg]2− | ||
722(0.5), 721(0.5) | 2[dmaphPc]− |
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Breza, M. DFT Studies of Dimethylaminophenyl-Substituted Phthalocyanine and Its Silver Complexes. Molecules 2024, 29, 1344. https://doi.org/10.3390/molecules29061344
Breza M. DFT Studies of Dimethylaminophenyl-Substituted Phthalocyanine and Its Silver Complexes. Molecules. 2024; 29(6):1344. https://doi.org/10.3390/molecules29061344
Chicago/Turabian StyleBreza, Martin. 2024. "DFT Studies of Dimethylaminophenyl-Substituted Phthalocyanine and Its Silver Complexes" Molecules 29, no. 6: 1344. https://doi.org/10.3390/molecules29061344