*2.3. Synthesis*

*Bis*-thyrazine-Sn(IV)-5,10,15,20-tetra(4-sulfonatophenyl)porphyrin (I) was obtained according to the procedure described by us previously in [30] from the bis-hydroxy-Sn(IV)-5,10,15,20-tetra(4-sulfonatophenyl)porphyrin (III). Mass-spectrum (MALDI-TOF): (m/z):[M+H]+ 1407.17; molecular formulaC62H46N6O18S4Sn-requires [M]+1406.01;UV-Vis (H2O), λnm (lgε): 594 (4.06), 555 (3.57), 421 (5.04), 1HNMR (500 MHz, D2O), ppm: 9.41 (s, 8H, Hβ-pyr.), 8.72 (s, 4H, NH2-L), 8.36 (d, J = 7.8, 8H, ortho-C6H4), 8.14 (d, J = 7.8, 8H, meta-C6H4), 5.51 (d, 4H, ortho-Ar-L), 4.37 (t, 2H, CH-L),3.19(m, 4H, CH2-L), 2.28 (d, 4H, meta-Ar-L);IR-spectrum, (KBr), ν, cm<sup>−</sup>1:3420 (sb)ν (OH), 3143 (b) ν (NH3+str.), 2939(w),ν(C-H, Ar), 2814(w),ν(C-H, Ar), 1680 (b)ν(C=C, Ar), 1655 (b) ν (NH3+deg. def.), 1607 (s)ν (COO- assym.), 1561(b)ν(C=C, Ph), 1517 (m)νNH3+sym. def.),1384 (s) ν (COOsym.), 1367 bν(C=N), 1337 (w)ν (C-N, Por), 1246–45 (m) (NH3+rocking,),ν(C-N), 1200(w), (C-N, Pr), 1197 (m), 1128 (m), 1116(m)δ(C-H), 1045(m)ν(S-C), 1015(m) δ(C-H), 998 (m) ν(C-C),842–41, 744 (w)γ(C-H, Pyr), 706(w)γ(C-H, Ph), 706(w)γ(C-H, Ph), 646 (m) (COOwagging), 580m(COO- rocking), 562 (m) ν(Sn-O).

*Bis*-diaminohydroquinone-Sn(IV)−5,10,15,20-tetra(4-sulfonatophenyl)porphyrin (II) was synthesized similarly to (I): 7.38 mg of III (0.0068 mmol) and 3.62 mg of 2,5-diaminohydroquinone dihydrochloride (0.017 mmol) were dissolved in 20 mL of distilled water. The resulting solution was boiled for 5 h, cooled, and then evaporated to dryness in a vacuum. The product was purified by column chromatography on neutral alumina using an ethanol-water mixture (1:2) as the eluent. The product yield after recrystallization was equal to 93%.Mass-spectrum (MALDI-TOF): (m/z):[M+H]+ 1325.39; molecular formula C56H38N8O16S4Sn-requires [M]<sup>+</sup> 1324.01; UV-Vis (H2O), λmax (logε) nm:419 (5.11),554 (4.10), 593 (3.61);1H NMR, (500 MHz, D2O): 9.10 (s, 8H,β-pyrr.), 8.45 (d, J = 7.8 Hz, 4H, ortho-C6H5), 8.25 (d, J = 7.7 Hz, 8H, meta-C6H5), 8.59 (s, br, 2H, NH2 (L)), 5.32 (s, br, 2H, NH2 (L)), 5.97(t, J = 8.0 Hz, 2H, Ar(L)), 4,90 (s, 2H, OH(L)), 2.92 (t, J = 2.0 Hz, 2H (L)).IR-spectrum, (KBr), ν, cm<sup>−</sup>1:3357 (sb)ν (N-H), 3244 (sb)ν (O-H) ν, 3052,2930-ν (C-H, Ar), 1695(b)ν(C=C, Ar), 1619(N-H)δ, 1582(b)ν(C=C, Ph), 1601, 1501, 1478 (C-C, Ar) ν, 1381 bν(C=N, Por), 1359 (w)ν (C-N, Por), 1152 (C-O)ν, 1045(m)ν(S-C), 1015(m) δ(C-H), 998 (m) ν(C-C), 821, 7 50 (C-H) γ, 784 (N-H) γw, 699 (C-C)γ, 566 (m) ν(Sn-O).

*Bis-*hydroxy-Sn(IV)-5,10,15,20-tetra(4-sulfonatophenyl)porphyrin (III) was synthesized according to the method described by the authors of [31]. Mass-spectrum (MALDI-TOF): (m/z):[M+H]+ 1081.23; molecular formula C44H26N4O14S4Sn-requires [M]+ 1080.02;UV-Vis (H2O), λ max(logε) nm: 593 (4.10), 554 (3.60), 419 (5.40), 1H NMR, (500 MHz, D2O): 9.10 (s, 8H,β-pyrr.), 8.45 (d, J = 7.8 Hz, 4H, ortho-C6H5), 8.25 (d, J = 7.7 Hz, 8H, meta-C6H5). −7.02 (2H, OH).

The synthesis of dimeric (I-Cu-I, II-Cu-II), oligomeric (Cu-[I-Cu]6 and Cu-[II-Cu]6) and polymers ([I-Cu]n and [II-Cu]n) porphyrins was carried out by heating an aqueous solution of the corresponding axial complex I or II and copper chloride. The concentration of the complexes was at least 5 × 10−<sup>4</sup> mol/L.

Synthesis of I-Cu-I, Cu-[I-Cu]6 and [I-Cu]n: 13.5 mg (0.0096 mmol) of complex I was dissolved in 10 mL of distilled water. Then, 1.63 mg (0.0096 mmol) or 8.2 mg (0.0480 mmol) of copper chloride dihydrate was added to the resulting solution to obtain a molar ratio of I-Cu2+ equal to 1:1 or 1:5, respectively. To suppress hydrolysis, the reaction mixture was acidified with several drops of diluted hydrochloric acid. The resulting reaction mixtures were heated for 24 h at a temperature of 85–90 ◦C. After the reaction was completed, the soluble and insoluble reaction products were separated by filtration at atmospheric pressure. The insoluble reaction product ([I-Cu]n) was repeatedly washed with distilled water on a filter.

Synthesis of II-Cu-II, Cu-[II-Cu]6,and [II-Cu]n: 12.5 mg (0.0094 mmol) of complex II was dissolved in 10 mL of distilled water. Then, 1.6 mg (0.0094 mmol) or 8.0 mg (0.0471 mmol) of copper chloride dihydrate was added to the resulting solution to obtain a molar ratio of II-Cu2+ equal to 1:1 or 1:5, respectively. The rest of the procedure was similar to the synthesis of polymers and oligomers of I with Cu2+.
