Copper(I)-induced formation of an organic sandwich structure. Structural hypothesis for luminescence of binuclear copper bipyrimidine complexes

, , , , , und . Angewandte Chemie 101 (12): 1734--1735 (1989)


(m-Bpym)Cu(PR3)22(BF4)2 (I; bpym = bipyrimidine; R = Ph, C6D5, o-, m- and p-MeC6H4, C6F5, p-ClC6H4, p-Me2NC6H4), (m-bpym)Cu(PR1R22)22(BF4)2 (II; R1 = H, Me, R2 = Ph; R1 = p-MeC6H4, R2 = Me) and (m-bpym)Cu(Ph2P(CH2)nPPh2)2(BF4)2 (III; n = 1-5) were prepd. from Cu, Cu(BF4)2, bpym and phosphine in MeOH under reflux. I.MeOH.H2O (R = Ph) is triclinic, space group P1̅, a 1192.4(2), b 1253.7(3), c 1457.3(3) pm, a 65.57(2), b 71.76(2), g 74.88(2)°, Z = 1, dc = 1.34 g cm-3, R = 0.039, Rw = 0.035. I.MeOH.H2O (R = Ph) has intense luminescence in the solid state which in soln. is not intense before or after anion exchange with PF6- or ClO4-; I (R $\not=$ Ph, C6D5, or m-MeC6H4) and II do not luminesce. I (R = C6D5, m-MeC6H4), the Ph3As analog of I and III (n = 5) have similar luminescent properties in the solid state. For I.MeOH.H2O (R = Ph) the intramol. Cu-Cu distance is 562.2 pm and the intermol. Cu-Cu distance is \textgreater953.3 pm. The space across the bridging bpym ligand is so large that the Ph ring of Ph3P is involved in p-exchange interaction with the p-acceptor heterocycle bpym. This allows luminescence to occur. on SciFinder(R)

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