Crystal and molecular structure of [Cu(bcp)2]BF4.cntdot.CH3OH (bcp = 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)

Homoleptic tetraazaphenanthrene-based copper(I) complexes: Synthesis, spectroscopic characterization, crystal structures and computational studies

“…A shoulder on the red side of the absorption maximum has been assigned to low-lying MLCT transitions. The shoulder arises when either static or dynamic flattening distortion induces D 2d to D 2 symmetry transformation as reported previously [55][56][57]. According to the previous theoretical calculations (DFT) [56], the MLCT excited state flattening from the pseudo D 2d to D 2 symmetry effectively splits the nearly degenerate Cu 3d xz and 3d yz HOMO orbitals.…”

“…The shoulder arises when either static or dynamic flattening distortion induces D 2d to D 2 symmetry transformation as reported previously [55][56][57]. According to the previous theoretical calculations (DFT) [56], the MLCT excited state flattening from the pseudo D 2d to D 2 symmetry effectively splits the nearly degenerate Cu 3d xz and 3d yz HOMO orbitals. These changes in 3d MO energy levels translate into an increased energy splitting between the two observed 1 MLCT transitions that involve them, leading to a red-shift of the low-energy shoulder and a blue-shift of the main MLCT absorption peak.…”

Electron Transfer by Copper Centers

“…McMillin's group 110 has also reported that the crystal structure of Cu I (dpmp) 2 (dpmp ) 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline ) bathocuproin) exhibited a nearly perfect tetrahedral geometry with a dihedral angle of 87.6°. A number of related Cu(I) structures have also been reported by this group, 111 and the various types of distortions have been discussed.…”

Multispectroscopic DNA-binding studies of a tris-chelate nickel(II) complex containing 4,7-diphenyl 1,10-phenanthroline ligands

“…Intercalation, in which two phenyl rings of the ligand are inserted into the DNA base pairs, may be less favorable, because the sheer size of the DIP ligand would preclude simultaneous intercalation of both phenyl rings as the diameter of the ligand is much larger than the width of base pairs. In addition, the crystal structure data of solid [Ru(DIP) 3 ] 2+ [17] and [Cu(bcp) 2 ] BF4 (bcp = 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) [40] complexes show that all the phenyl groups are skewed about 40°out of phenanthroline plane owing to steric effect between hydrogen atoms in the phenyl and phenanthroline rings. Intercalation of the entire DIP moiety thus would require that the phenyl groups rotate into the plane of the phenanthroline moiety in order to minimize stacking.…”