Intense Photosensitized Emission from Stoichiometric Compounds Featuring Mn(2+) in Seven- and Eightfold Coordination Environments.
Synthetic, structural and luminescence studies of stoichiometric crown ether compounds of Mn(2+) in well-defined coordination environments were undertaken in an effort to understand the origin of emitting crystal defects found in cubic F23 [(K18C6)(4)MnBr(4)][TlBr(4)](2) crystals (Fender, N. S.; et al. Inorg. Chem. 1997, 36, 5539). The new compound [Mn(12C4)(2)][MnBr(4)](2)[N(CH(3))(4)](2) (3) features Mn(2+) ions in eight- and fourfold coordination environments of [Mn(12C4)(2)](2+) and MnBr(4)(2)(-) respectively, while Mn(2+) in [Mn(15C5)(H(2)O)(2)][TlBr(5)] (4) is in the sevenfold coordination polyhedron of [Mn(15C5)(H(2)O)(2)](2+). Crystal data for 3: monoclinic, P2(1)/c (No. 14); a = 14.131(3) Å, b = 12.158(1) Å, c = 14.239(2) Å, beta = 110.37(1) degrees, Z = 2, R1 = 0.039 and wR2 = 0.083. For 3, long-lived emission (77 K decay rate approximately 3 x 10 s(-)(1)) from [Mn(12C4)(2)](2+) (the first for eight-coordinate Mn(2+) in stoichiometric compounds) is observed (lambda(max) approximately 546 nm) along with that of the sensitizing MnBr(4)(2)(-) (lambda(max) approximately 513 nm), which is partially quenched. Emission from the seven-coordinate [Mn(15C5)(H(2)O)(2)](2+) species of 4 and [Mn(15C5)(H(2)O)(2)][MnBr(4)] (the first for seven-coordinate Mn(2+) in stoichiometric compounds) peaks at lambda(max) approximately 592 nm. Unusually intense absorptions attributable to the seven-coordinate species are observed at 317 ((2)T(2)((2)I) <-- (6)A(1)), 342 ((4)T(1)((4)P) <-- (6)A(1)), 406 ((4)E((4)G) <-- (6)A(1)), and 531 ((4)T(1)((4)G) <-- (6)A(1)) nm.
Reid
Howard O. N.
HO
Chemical Crystallography Laboratory, Chemistry Department, Imperial College of Science, Technology and Medicine, South Kensington, London SW7 2AY, U.K.
Kahwa
Ishenkumba A.
IA
White
Andrew J. P.
AJ
Williams
David J.
DJ