Aggregation-induced emissive copper(I) complexes for living cell imaging.

Phosphorescent binuclear copper(I) complexes [Cu2(BrphenBr)2(Ph2P(CH2)nPPh2)2](ClO4)2 with different conformations are obtained by reaction of [Cu(NCCH3)4]ClO4, 3,8-dibromo-1,10-phenanthroline (BrphenBr), and corresponding diphosphine ligands, where n = 1, 4, 5, and 6 in complexes Cu-1, Cu-2, Cu-3, and Cu-4, respectively. Complex Cu-4 exhibits both the eclipsed and the staggered conformations of 18-membered Cu2C12P4 metallacycles in a 1:1 ratio in the crystal structure. All complexes are very stable to air and moisture in the solid state because of the high level of protection of all the Cu(I) centers, N and P atom centers resulting from the close contact of BrphenBr and diphosphine ligands, and what is more important is that there exist very soft P donors and the chelating effect of aromatic N atoms. The ESI-MS result through changing the collision cell energy from 0 to 20 eV suggests that the corresponding [Cu2(Ph2P(CH2)nPPh2)2](2+) cations are the thermodynamically stable species, while [Cu2(BrphenBr)2(Ph2P(CH2)nPPh2)2](ClO4)2 are stable products in crystallization kinetics in solutions. All complexes Cu-1-Cu-4 display good aggregation-induced phosphorescence emission (AIPE) behavior in CH2Cl2/hexane mixed solvents, which are suggested to arise from restriction of intramolecular rotation. Aggregation-induced emission (AIE) of complexes Cu-1-Cu-4 in PBS/DMSO (99:1, v:v) is used for living HeLa cell imaging successfully with green intracellular emission image.

Dual luminescent tetranuclear organogold(I) macrocycles of 5,5'-diethynyl-2,2'-bipyridine and their efficient sensitization of Yb(III) luminescence.

Reaction of (AuC≡CbpyC≡CAu)(n) (HC≡CbpyC≡CH = 5,5'-diethynyl-2,2'-bipyridine) with diphosphine ligands Ph(2)P(CH(2))(n)PPh(2) (n = 1 dppm, 3 dppp, 5 dpppen, 6 dpph), 1,1'-bis(diphenylphosphino)ferrocene (dppf), and 1,2-bis(diphenylphosphino)benzene (bdpp) in CH(2)Cl(2) afforded the corresponding dual luminescent gold(I) complexes [(AuC≡CbpyC≡CAu)(2)(µ-dppm)(2)] (1), [(AuC≡CbpyC≡CAu)(2)(µ-dppp)(2)] (2), [(AuC≡CbpyC≡CAu)(2)(µ-dpppen)(2)] (3), [(AuC≡CbpyC≡CAu)(2)(µ-dpph)(2)] (4), [(AuC≡CbpyC≡CAu)(2)(µ-dppf)(2)] (5), and [(AuC≡CbpyC≡CAu)(2)(µ-bdpp)(2)] (6). The solid structures of complexes 1 and 2 are confirmed to be tetranuclear macrocyclic rings by single crystal structure analysis, and those of complexes 3-6 are proposed to be similar to those of complexes 1 and 2 in structure because their good solubility in CH(2)Cl(2), their HRMS results, and the P···P separations of 20.405-20.697 Å in the same linear rigid P-Au-C≡CbpyC≡C-Au-P unit are all favorable to form such 2:4:2 macrocycles. Each of the absorption spectral titrations between complexes 1-6 and Yb(hfac)(3)(H(2)O)(2) (Hhfac = hexafluoroacetylacetone) gives a 2:1 ratio between the Yb(hfac)(3) unit and the complex 1-6 moieties. The energy transfer occurs efficiently from the gold(I) alkynyl antennas 1-6 to Yb(III) centers with the donor ability in the order of 1 ~ 2 ~ 3 ~ 4 > 6 > 5.