Molecular Engineering to Tune Functionality: The Case of Cl-Substituted [Fe(terpy)2]2+hdl:21.15109/CONCORDA/VF4I94ARP2023-11-081Papp, Mariann; Keszthelyi, Tamás; Vancza, Andor; Bajnóczi, G. Éva; Kováts, Éva; Németh, Zoltán; Bogdán, Csilla; Bazsó, Gábor; Rozgonyi, Tamás; Vankó, György, 2023, "Molecular Engineering to Tune Functionality: The Case of Cl-Substituted [Fe(terpy)2]2+", https://hdl.handle.net/21.15109/CONCORDA/VF4I94, ARP, V1Molecular Engineering to Tune Functionality: The Case of Cl-Substituted [Fe(terpy)2]2+hdl:21.15109/CONCORDA/VF4I94Papp, MariannKeszthelyi, TamásVancza, AndorBajnóczi, G. ÉvaKováts, ÉvaNémeth, ZoltánBogdán, CsillaBazsó, GáborRozgonyi, TamásVankó, GyörgyVEKOP-2.3.2-16-2017-000152018-1.2.1-NKP-2018-00012FK 124460PD 131845ARPBuzsaki, DanielBuzsaki, Daniel2023-10-10ChemistryPhysicsOptimized molecular geometriesOptimized molecular energiesSchemes on the synthesis of the ligandsNMR spectraMössbauer spectraCyclic VoltammetryThe properties of transition-metal complexes and their chemical dynamics can be effectively modified with ligand substitutions, and theory can be a great aid to such molecular engineering. In this paper, we first theoretically explored how substitution with a Cl atom at different positions of the terpyridine ligand affects the electronic structure of the [Fe(terpy)₂]²⁺ complex. We found that besides the substitution at position 4′, the next most promising candidate to cause substantial electronic effects is that where the side pyridine ring is substituted at position 5 (β). Therefore, next, we examined in detail the Fe(II) complexes of the 5-chloro and 5,5″-dichloro derivatives of terpy, theoretically and experimentally, to reveal how these substitutions modify the ground state properties and the lifetime of the excited quintet state in such complexes. In addition, we extend the investigation to the complexes of the analogously substituted derivatives of 4′-SMe-terpy. The substitution at position(s) 5 (and 5″) with Cl lowers the energy of the quintet state and increases its lifetime; the results on the 4′-SMe-substituted complexes show similar changes with these two substitutions, verifying that these effects are more or less additive. This study contributes to the enhancement of our molecular engineering toolset for modifying the potential energy landscape of similar complexes.@article{doi:10.1021/acs.inorgchem.3c00271, author = {Papp, Mariann and Keszthelyi, Tamás and Vancza, Andor and Bajnóczi, Éva G. and Kováts, Éva and Németh, Zoltán and Bogdán, Csilla and Bazsó, Gábor and Rozgonyi, Tamás and Vankó, György}, title = {Molecular Engineering to Tune Functionality: The Case of Cl-Substituted [Fe(terpy)2]2+}, journal = {Inorganic Chemistry}, volume = {62}, number = {16}, pages = {6397-6410}, year = {2023}, doi = {10.1021/acs.inorgchem.3c00271}, note ={PMID: 37039430}, eprint = { https://doi.org/10.1021/acs.inorgchem.3c00271 } }10.1021/acs.inorgchem.3c00271@article{doi:10.1021/acs.inorgchem.3c00271, author = {Papp, Mariann and Keszthelyi, Tamás and Vancza, Andor and Bajnóczi, Éva G. and Kováts, Éva and Németh, Zoltán and Bogdán, Csilla and Bazsó, Gábor and Rozgonyi, Tamás and Vankó, György}, title = {Molecular Engineering to Tune Functionality: The Case of Cl-Substituted [Fe(terpy)2]2+}, journal = {Inorganic Chemistry}, volume = {62}, number = {16}, pages = {6397-6410}, year = {2023}, doi = {10.1021/acs.inorgchem.3c00271}, note ={PMID: 37039430}, eprint = { https://doi.org/10.1021/acs.inorgchem.3c00271 } }<br> Papp M, Keszthelyi T, Vancza A, Bajnóczi ÉG, Kováts É, Németh Z, et al. Molecular engineering to tune functionality: the case of Cl substituted [Fe(terpy)2]2 . ChemRxiv. Cambridge: Cambridge Open Engage; 2022; This content is a preprint and has not been peer-reviewed.10.26434/chemrxiv-2022-4645x<br> Papp M, Keszthelyi T, Vancza A, Bajnóczi ÉG, Kováts É, Németh Z, et al. Molecular engineering to tune functionality: the case of Cl substituted [Fe(terpy)2]2 . ChemRxiv. 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