An Insight of the Results Provided by Color-Tuning Studies Made on Ir(III) Complexes: A pi-Neutral CF3Group Viewed by Adjusting Energies of pi-type Molecular Orbitals

Autor:	Fu Yung Huang, Hung Sung Lin, Shou Yun Lu, Shao-Pin Wang, Wei Lin Su, Yan Wu
Rok vydání:	2015
Předmět:	Ligand field theory Negative hyperconjugation Crystallography Computational chemistry Chemistry Molecular orbital diagram Molecular orbital theory Molecular orbital General Chemistry Orbital overlap HOMO/LUMO Natural bond orbital
Zdroj:	Journal of the Chinese Chemical Society. 62:939-943
ISSN:	0009-4536
DOI:	10.1002/jccs.201400271
Popis:	The pi-nature of a CF3 group can be understood through analysis of its bond orbitals (BOs) mixed into the pi-type molecular orbitals of CF3-substituted Ir(ppy)2MDPA+ complexes (ppy=2-phenyl-pyridine and MDPA=methylated 2,2′-dipyridyl amine). It has been found that, through this natural bond orbital analysis, the parent’s molecular orbitals (MOs) can be stabilized by χρ*CF BO via negative hyperconjugation and, simultaneously, destabilized by electron lp(F) BO. Since these two competing pi-effects are virtually counterbalanced as indicated by the vanishing values of crystal orbital overlap populations, the chemical substitution strategy originated from lowering of HOMO by using this electron-withdrawing CF3 group has been found effective in color-tuning to blue region. Based on reduced shielding effect due to de- creased χρ-electron density, the reported position dependent CF3-substitution effects on pi-type MOs can also be understood through HOMO/LUMO wavefunction analysis.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::0ad1b54c8fa9338f85ac9fdc514dd972 https://doi.org/10.1002/jccs.201400271 Zobrazit plný text záznamu Plný text ve formátu PDF Plný text ve formátu HTML
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