Abstract
The 2,2′:6′:2″-terpyridine ligand has literally shaped the coordination chemistry of transition metal complexes in a plethora of fields. Expansion of the ligand bite by amine functionalities between the pyridine units in the tridentate N,N’-dimethyl-N,N’-dipyridine-2-yl-pyridine-2,6-diamine ligand (ddpd) modifies the properties of corresponding transition metal complexes, comprising redox chemistry, molecular dynamics, magnetism and luminescence. The origins of these differences between ddpd and tpy complexes will be elucidated and comprehensively summarized with respect to first row transition metal complexes with d2–d10 electron configurations. Emerging applications of these ddpd complexes complementary to those of the well-known terpyridine ligand will be highlighted.
Highlights
Pincer-type [1,2] terpyridine ligands (2,20 :60,200 -terpyridine tpy; pincer ligands are tridentate, 6-electron donor ligands that enforce a meridional coordination geometry on the metal centre) and their manifold complexes [3] play a central role in key fields of coordination chemistry with important applications in supramolecular chemistry [4,5,6,7,8,9,10,11,12,13,14], spin-crossover (SCO) phenomena [15,16,17,18], homogeneous catalysis [19,20,21], biomedical applications [22], redox non-innocence [23,24,25,26,27] or photochemistry [6,7,28], to name just a few
Ni(CO)3(L) complexes revealed that the net donor strength (σ + π) of ddpd donor atoms ranks between that of trimethylamine and N-heterocyclic carbene ligands and is larger than that of pyridine, as estimated from the Density Functional Theory (DFT) calculated A 1 carbonyl stretching
According to single crystal X-ray diffraction and spectroscopic data, [V(tpy)2 ]0 features a [VIV2 ]0 electronic structure with an unpaired electron localized at the vanadium ion (S = 1/2 ) [90,154,155]. These data again illustrate the complementary nature of tpy and ddpd, with tpy stabilizing reduced, electron-rich vanadium species by internal redox reactions and ddpd stabilizing electron-poor vanadium(III) complexes
Summary
Pincer-type [1,2] terpyridine ligands (2,20 :60 ,200 -terpyridine tpy; pincer ligands are tridentate, 6-electron donor ligands that enforce a meridional coordination geometry on the metal centre) and their manifold complexes [3] play a central role in key fields of coordination chemistry with important applications in supramolecular chemistry [4,5,6,7,8,9,10,11,12,13,14], spin-crossover (SCO) phenomena [15,16,17,18], homogeneous catalysis [19,20,21], biomedical applications [22], redox non-innocence [23,24,25,26,27] or photochemistry [6,7,28], to name just a few.
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