Ivanovo, Ivanovo, Russian Federation
UDK 544.164 Взаимосвязь между химическим строением и оптическими свойствами. Взаимосвязь между химическим строением и способностью вещества к вращению плоскости поляризации поляризованного света, в том числе к магнитному вращению плоскости поляризации. Оптическая активность
UDK 544.42 Формальная кинетика
The paper concerns NH-bonds chemical activity exhibiting in porphyrin molecules typical of macrocycles with planar or non-planar polarized structures. It is not limited by the increasing rate of their metal complexing indicator reaction in proton-donating media in comparison with proton-donating ones. The work dwells on the entropy of the process towards more positive values as the electron-donating properties of the solvent increase. It is due to the formation of molecular complexes "porphyrin - electron-donor" increasing the solvation of the initial state of the complexing reaction. The deformation of the planar structure of the H2P macrocycle expressed by the example of N- and dodeca-substituted porphyrin accompanying by an appreciable polarization of the molecule does not lead to the appearance of NH-bonds chemical activity.
tetrapyrrole macroheterocyclic compounds; porphyrins; complexing reaction; chemical activity of NH bonds; activation entropy
1. Yacimirskiy K.B., Lampeka Ya.D. Fiziko-himiya kompleksov metallov s makrociklicheskimi ligandami. Kiev: Naukova Dumka, 1985. 256 s.
2. Berezin D.B. Makrociklicheskiy effekt i strukturnaya himiya porfirinov. M.: IGHTU: Krasand, 2010. 421 s.
3. Smirnov V.I., V'yugin A.I., Krestov G.A. Makrociklicheskiy effekt sol'vatacii porfirinov // Zhurn. fizich. himii. 1989. T. 63, № 8. S. 2245-2247.
4. Berezin D.B., Semeykin A.S., Berezin M.B. Vliyanie struktury makrocikla na sol'vataciyu neploskih porfirinov v organicheskih rastvoritelyah // Zhurn. fizich. himii. 2009. T. 83, № 8. S. 1480-1486.
5. Berezin B.D. Porfiriny: spektroskopiya, elektrohimiya, primenenie. M.: Nauka, 1987. S. 182-213.
6. Helevina O.G., Chizhova N.V., Berezin B.D. Osobennosti kompleksoobrazovaniya soley 3d-metallov s bromproizvodnym tetraazaporfina // Koord. himiya. 1991. T. 17, № 3. S. 400-404.
7. Golubchikov O.A., Puhovskaya S.G., Kuvshinova E.M. Uspehi himii porfirinov. SPb.: NII himii SPbGU, 2004. T. 4. S. 45-75.
8. Klyueva M.E., Lomova T.N., Berezin B.D. Pryamaya kolichestvennaya ocenka makrociklicheskogo effekta v processe dissociacii kompleksov protoporfirina // Koord. himiya. 2002. T. 28, № 11. S. 845-850.
9. Lomova T.N. Aksial'no koordinirovannye metalloporfiriny v nauke i tehnike. M.: URSS, 2018. 700 s.
10. Stuzhin P.A., Khelevina O.G. Azaporphyrins: structure of the reaction centre and reactions of complexformation // Coord. Chem. Rev. 1996. Vol. 147. P. 41-86. DOIhttps://doi.org/10.1016/0010-8545(94)01126-5.
11. Stuzhin P.A., Malyasova A.S., Kokareva E., Tarakanov P.A., Koifman O.I., Sheinin V.B. Acid-base properties of tetrapyrazinoporphyrazines. Deprotonation of octaethyltetrapyrazinoporphyrazine in CH2Cl2, THF, DMSO and pyridine. The crucial role of water // Dyes Pigm. 2017. Vol. 139. P. 509-516. DOI:https://doi.org/10.1016/j.dyepig.2016.12.047
12. Pukhovskaya S.G., Semeikin A.S., Syrbu S.A., Ivanova Y.B., Kruk N.N. Investigation of acidic and coordination properties of octabromo-substituted porphyrins in the system of 1,8-diazabicyclo[5,4,0]unde-7-ene-acetonitrile // Russ. J. Gen. Chem. 2019. Vol. 89, no. 6. P. 1286-1296. DOIhttps://doi.org/10.1134/S1070363219060252/
13. Pukhovskaya S.G., Nam D.T., Semeikin A.S., Syrbu S.A., Ivanova Y.B., Liulkovich L.S., Kruk M.M. Porphyrin acidity and metal ion coordination revisited: electronic substitution effects // J. Incl. Phenomena and Macrocyclic Chem. 2017. Vol. 89, no. 3-4. P. 325-332. DOI:https://doi.org/10.1007/s10847-017-0758-9
14. Petrov O.A. Kineticheskie zakonomernosti medlennogo perenosa protonov ot β-zameschennyh porfirazinov k organicheskim osnovaniyam // Zhurn. fizich. himii. 2021. T. 95, № 4. S. 549-557.
15. Berezin D.B. Kriterii ocenki sostoyaniya NH svyazey v molekulah porfirinov // Koord. himiya. 2007. T. 33, № 6. S. 476-480.
16. Berezin D.B., Berezin B.D. Chemical processes with participation of biological and related compounds. Leiden: Brill, 2008. P. 169-217.
17. Berezin D.B., Karimov D.R. Porphyrins and porphyrin analogs interactions with coordinating organic solvents // Macroheterocycles. 2009. Vol. 2, no. 1. P. 42-51.
18. Lihonina A.E., Berezin M.B., Krest'yaninov M.A., Berezin D.B., N-Svyazannye molekulyarnye kompleksy fenilzameschennyh porfirinoidov s elektronodonorami // Izv. vuzov. Himiya i him. tehnologii. 2021. T. 64, №. 10. S. 29-39. DOI:https://doi.org/10.6060/ivkkt.20216410.6464
19. Chirvony V.S., Sazanovich I.V., Galievsky V.A., van Hoek A., Schaafsma T.J., Malinovskii V.L., Holten D. Photophysical and structural properties of saddle-shaped free base porphyrins: evidence for an “orthogonal” dipole moment // J. Phys. Chem. 2001. Vol. 105, no. 32. P. 7818-7829. DOIhttps://doi.org/10.1021/JP010274O.
20. Senge M.O. Exercises in molecular gymnastics – bending, stretching and twisting porphyrins // Chem. Commun. 2006. P. 243-256. DOI:https://doi.org/10.1039/b511389j
21. Berezin D.B., Karimov D.R., Barannikov V.P., Semeykin A.S. Issledovanie termoustoychivosti porfirinov s himicheski aktivnoy NH-svyaz'yu i ih associatov s elektronodonornymi rastvoritelyami // Zhurn. fizich. himii. 2011. T. 85, № 12. S. 2325-2330.
22. Berezin D.B., Berezin M.B., Karimov D.R. Osobennosti sol'vatacii mezo-trifenilkorrola v organicheskih rastvoritelyah po dannym kalorimetrii // Zhurn. fizich. himii. 2013. T. 87, № 4. S. 615-620.
23. Berezin D.B., Krest'yaninov M.A. Stroenie N-associatov porfirinov, invertirovannyh porfirinoidov i korrolov s N,N-dimetilformamidom // Zhurn. strukturn. himii. 2014. T. 55, № 5. S. 812-830.
24. Berezin B.D. Coordination compounds of porphyrins and phthalocyanines. J. Wiley Publ.: New York-Toronto 1981. 286 p.
25. Ivanova Y.B., Mamardashvili N.Z., Koifman O.I., Pukhovskaya S.G., Kruk M.M. Rate-acidity hysteresis and enthalpy-entropy compensation upon metalloporphyrin formation: implication for the metal ion coordination mechanism // J. Mol. Liq. 2019. Vol. 275. P. 491-498. DOIhttps://doi.org/10.1016/J.MOLLIQ.2018.11.107
26. Kruk N.N., Puhovskaya S.G., Ivanova Yu.B., Koyfman O.I. Ental'piyno-entropiynaya kompensaciya pri koordinacii iona metalla porfirinami: obobschenie dlya svobodnyh osnovaniy i dvazhdy deprotonirovannyh makrociklov // Izv. akad. nauk. Seriya himicheskaya. 2020. № 6. S. 1072-1075.
27. Berezin D.B., Bazlova I.Yu, Malkova O.V., Andrianov V.G. Vliyanie faktorov iskazheniya i aromatizacii na kinetiku kompleksoobrazovaniya tetrapirrol'nyh makrociklov v acetonitrile // Koord. himiya. 2000. T. 26, № 4. S. 315-319.
28. Karimov D.R., Berezin D.B., Tomilova I.K., Korroly kak aromaticheskie analogi korrinoidov i vitamina V12: sintez, strukturnye osobennosti i svoystva makrogeterociklov, perspektivy himii materialov na ih osnove // Ot himii k tehnologii shag za shagom. 2020. T. 1, № 1. P. 9-55. DOI:https://doi.org/10.52957/27821900_2020_01_9.
29. Lavallee D.K. The chemistry and biochemistry of N-substituted porphyrins. New York, N.Y.: VCH Publishers, 1987. 313 p.
30. Berezin D.B., Andrianov V.G., Semeykin A.S. Proyavlenie strukturnyh osobennostey molekul porfirinov v ih elektronnyh spektrah pogloscheniya // Optika i spektroskopiya. 1996. T. 80, № 4. S. 618-626.
31. Burger K. Sol'vataciya, ionnye reakcii i kompleksoobrazovanie v nevodnyh sredah. M.: Mir, 1984. 256 s.
32. Berezin D.B., Zharnikova N.V., Andrianov V.G., Shatunov P.A., Semeykin A.S. Processy koordinacii N-zameschennyh porfirinov prostymi i helatnymi solyami cinka v DMSO // Koord. himiya. 2002. T. 28, № 5. S. 348-355.
33. Berezin D.B., Toldina O.V. Vliyanie protonodonornogo rastvoritelya na protekanie reakcii kompleksoobrazovaniya klassicheskih i neklassicheskih porfirinov v srede piridina // Zhurn. neorganich. himii. 2002. T. 47, № 12. S. 2075-2081.
34. Berezin D.B., Toldina O.V., Kumeev R.S. Aktivaciya NH svyazey v molekulah tetrabenzoporfirinov elektronodonornymi rastvoritelyami // Zhurn. fizich. himii. 2004. T. 78, №. 8. S. 1427-1432.
35. Berezin D.B., Makarov V.V., Plotnikova T.A., Kruchin S.O., Kumeev R.S., Romanenko Yu.V., Hudyaeva I.S., Belyh D.V. Spektral'nye harakteristiki proizvodnyh metilfeoforbida a, hlorina e6 i ih kompleksoobrazovanie s Su(II): vliyanie strukturnyh fragmentov molekul i prirody rastvoritelya // Zhurn. obschey himii. 2016. T. 86, № 7. S. 1195-1202.
36. Sazanovich I.V., van Hoek A., Panarin A.Yu., Bolotin V.L., Semeykin A.S., Berezin D.B., Chirvony V.S. The photophysical and metal coordination properties of the N-CH3 substituted porphyrins: H(NCH3)TPP VS H(NCH3)OEP // J. Porph. Phthaloc. 2005. Vol. 9, no. 1. P. 59-67.
