Chromophore-Functionalized Phenanthro-diimine Ligands and Their Re(I) Complexes

Inorganic Chemistry
Kristina S KiselIgor O Koshevoy

Abstract

A series of diimine ligands has been designed on the basis of 2-pyridyl-1 H-phenanthro[9,10- d]imidazole (L1, L2). Coupling the basic motif of L1 with anthracene-containing fragments affords the bichromophore compounds L3-L5, of which L4 and L5 adopt a donor-acceptor architecture. The latter allows intramolecular charge transfer with intense absorption bands in the visible spectrum (lowest λabs 464 nm (ε = 1.2 × 104 M-1 cm-1) and 490 nm (ε = 5.2 × 104 M-1 cm-1) in CH2Cl2 for L4 and L5, respectively). L1-L5 show strong fluorescence in a fluid medium (Φem = 22-92%, λem 370-602 nm in CH2Cl2); discernible emission solvatochromism is observed for L4 and L5. In addition, the presence of pyridyl (L1-L5) and dimethylaminophenyl (L5) groups enables reversible alteration of their optical properties by means of protonation. Ligands L1-L5 were used to synthesize the corresponding [Re(CO)3X(diimine)] (X = Cl, 1-5; X = CN, 1-CN) complexes. 1 and 2 exhibit unusual dual emission of singlet and triplet parentage, which originate from independently populated 1ππ* and 3MLCT excited states. In contrast to the majority of the reported Re(I) carbonyl luminophores, complexes 3-5 display moderately intense ligand-based fluorescence from an anthracene-...Continue Reading

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Citations

Mar 18, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Anna M MarońBarbara Machura

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Methods Mentioned

BETA
X-ray
NMR
phosphorescence

Software Mentioned

WinGX
APEX2
SADABS
PLATON
SHELXS
CrysAlisPro
SCALE3 ABSPACK
SQUEEZE
Gaussian

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