Azadipyrromethene Complexes of d8 Metal Centers Rhodium I Iridium I Palladium II and Platinum II        
Yazarlar (2)
Prof. Dr. Nihal DELİGÖNÜL Case Western Reserve University, Amerika Birleşik Devletleri
Thomas G. Gray
Case Western Reserve University, Amerika Birleşik Devletleri
Makale Türü Özgün Makale
Makale Alt Türü SSCI, AHCI, SCI, SCI-Exp dergilerinde yayınlanan tam makale
Dergi Adı Inorganic Chemistry
Dergi ISSN 0020-1669 Wos Dergi Scopus Dergi
Dergi Tarandığı Indeksler SCI-Expanded
Dergi Grubu Q4
Makale Dili İngilizce
Basım Tarihi 11-2013
Cilt No 52
Sayı 22
Sayfalar 13048 / 13057
DOI Numarası 10.1021/ic4017239
Makale Linki http://pubs.acs.org/doi/abs/10.1021/ic4017239
Özet
Azadipyrromethenes are blue pigments that chelate main-group and d-block Lewis acids. Reported here are azadipyrromethene complexes of d(8) metal centers. The new compounds are prepared in salt metathesis reactions with chlorinated organometallic precursors. Sixteen new complexes are reported. The principal absorption features are an intense peak near 600 nm and transitions in the ultraviolet; all are characteristic of the azadipyrromethene chromophore. All compounds are dark solids that yield blue or blue-violet solutions. Ten complexes are crystallographically characterized. The structures uniformly show backbone strain, with a meso-nitrogen atom that dilates from pure sp(2)-hybridization. Structural comparisons are made to related dipyrromethene and tetra-azaporphyrin complexes. The electron-donating capacity of azadipyrromethene ligands is evaluated from C≡O stretching frequencies of three rhodium(I) carbonyl complexes and from density-functional theory calculations. Frontier orbitals are confined to the azadipyrromethene ligand. HOMO-LUMO energy gaps are almost unperturbed from those of the free, anionic azadipyrromethene.
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