Oligophosphine-thiocyanate Copper(I) and Silver(I) Complexes and Their Borane Derivatives Showing Delayed Fluorescence.

The series of chelating phosphine ligands, which contain bidentate P2 (bis[(2-diphenylphosphino)phenyl] ether, DPEphos; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, Xantphos; 1,2-bis(diphenylphosphino)benzene, dppb), tridentate P3 (bis(2-diphenylphosphinophenyl)phenylphosphine), and tetradentate P4 (tris(2-diphenylphosphino)phenylphosphine) ligands, was used for the preparation of the corresponding dinuclear [M(µ2-SCN)P2]2 (M = Cu, 1, 3, 5; M = Ag, 2, 4, 6) and mononuclear [CuNCS(P3/P4)] (7, 9) and [AgSCN(P3/P4)] (8, 10) complexes. The reactions of P4 with silver salts in a 1:2 molar ratio produce tetranuclear clusters [Ag2(µ3-SCN)(t-SCN)(P4)]2 (11) and [Ag2(µ3-SCN)(P4)]22+ (12). Complexes 7-11 bearing terminally coordinated SCN ligands were efficiently converted into derivatives 13-17 with the weakly coordinating -SCN:B(C6F5)3 isothiocyanatoborate ligand. Compounds 1 and 5-17 exhibit thermally activated delayed fluorescence (TADF) behavior in the solid state. The excited states of thiocyanate species are dominated by the ligand to ligand SCN → π(phosphine) charge transfer transitions mixed with a variable contribution of MLCT. The boronation of SCN groups changes the nature of both the S1 and T1 states to (L + M)LCT d,p(M, P) → π(phosphine). The localization of the excited states on the aromatic systems of the phosphine ligands determines a wide range of luminescence energies achieved for the title complexes (λem varies from 448 nm for 1 to 630 nm for 10c). The emission of compounds 10 and 15, based on the P4 ligand, strongly depends on the solid-state packing (λem = 505 and 625 nm for two crystalline forms of 15), which affects structural reorganizations accompanying the formation of electronically excited states.

A silver metal complex as a luminescent probe for enzymatic sensing of glucose in blood plasma and urine.

In this work, we present a facile preparation of a paper-based glucose assay for rapid, sensitive, and quantitative measurement of glucose in blood plasma and urine. Two copper phosphorescent complexes [Cu(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)(2,6-dimethylphenylisocyanide)2][B(C6H3(CF3)2)4] (Cu1) and [Cu(2,9-dimethyl-1,10-phenanthroline)(2,6-dimethylphenylisocyanide)2][B(C6H3(CF3)2)4] (Cu2) and a new silver congener [Ag(P3)CNAg(P3)][B(C6H3(CF3)2)4] (Ag3) (P3 = PPh2C6H4-PPh-C6H4PPh2 [bis(o-diphenylphosphinophenyl)phenylphosphine]) have been synthesized and their oxygen sensing abilities were investigated. The dimetallic phosphine-based Ag3 complex, having a high oxygen sensing ability, was employed as an efficient signal transducer in enzymatic reactions to recognize blood plasma glucose and urine glucose, which provided a wide linear response for a concentration range between 1.0 and 35 mM and a rapid response, with a limit of detection (LOD) of 0.09 mM for glucose. In practical application, this Ag3 paper-based device offers great analytical reliability and accuracy upon monitoring glucose concentrations in blood plasma.

Adjustable coordination of a hybrid phosphine-phosphine oxide ligand in luminescent Cu, Ag and Au complexes.

A potentially tridentate hemilabile ligand, PPh2-C6H4-PPh(O)-C6H4-PPh2 (P(3)O), has been used for the construction of a family of bimetallic complexes [MM'(P(3)O)2](2+) (M = M' = Cu (1), Ag (2), Au (3); M = Au, M' = Cu (4)) and their mononuclear halide congeners M(P(3)O)Hal (M = Cu (5-7), Ag (8-10)). Compounds 1-10 have been characterized in the solid state by single-crystal X-ray diffraction analysis to reveal a variable coordination mode of the phosphine-oxide group of the P(3)O ligand depending on the preferable number of coordination vacancies on the metal center. According to the theoretical studies, the interaction of the hard donor P[double bond, length as m-dash]O moiety with d(10) ions becomes less effective in the order Cu > Ag > Au. 1-10 exhibit room temperature luminescence in the solid state, and the intensity and energy of emission are mostly determined by the nature of metal atoms. The photophysical characteristics of the monometallic species were compared with those of the related compounds M(P(3))Hal (11-16) with the non-oxidized ligand P(3). It was found that in the case of the copper complexes 5-7 the P(3)O hybrid ligand introduces effective non-radiative pathways of the excited state relaxation leading to poor emission, while for the silver luminophores the P[double bond, length as m-dash]O group leads mainly to the modulation of luminescence wavelength.

Luminescent Triphosphine Cyanide d(10) Metal Complexes.

Coinage metal cyanides efficiently react with a triphosphine. PPh2C6H4-PPh-C6H4PPh2 (P(3)). to give the complexes M(P(3))CN, where M = Cu (1), Ag (2), and Au (3), which can further interact with coordinatively unsaturated metal centers [M(P(3))](+) to give the homobimetallic [(P(3))M-CN-M(P(3))](+)X(-) [M = Cu (4a with X(-) = CF3SO3(-) and 4b with X(-) = BF4(-)), Ag (5)] or heterometallic [(P(3))Au-CN-Ag(P(3))](+) (6) species. Extension of this approach also provided the trinuclear complex [(P(3))Cu-NC-Au-CN-Cu(P(3))](+) (7). Compounds 1-5 were characterized in the solid state by X-ray crystallography. The NMR spectroscopic studies revealed that all of the complexes except 6 retain their structures in solution. The title compounds are luminescent in the solid state, with quantum yields ranging from 8 to 87%. The observed photoemission originates mainly from the metal-to-ligand charge-transfer states according to time-dependent density functional theory computational studies. The crystalline bimetallic Cu complexes 4a/4b demonstrate extremely high sensitivity of the emission intensity to molecular O2 (KSV1 = 639 atm(-1) and LOD = 0.010% for 3 times the signal-to-noise ratio).

Alkynyl triphosphine copper complexes: synthesis and photophysical studies.

A rigid triphosphine PPh2C6H4-PPh-C6H4PPh2 () reacted with Cu(+) and a stoichiometric amount of terminal alkyne under basic conditions to give a family of copper(i) alkynyl compounds [Cu()C[triple bond, length as m-dash]CR]. The number of terminal -C[triple bond, length as m-dash]CH groups in the starting ligand determines the nuclearity of the resulting complexes giving mono- (, R = Ph; , R = C6H4OMe; , R = C6H4NO2; , R = C6H4CF3; , R = 2-pyridyl), di- (R = -(C6H4)n-, n = 1 (), n = 2, (), n = 3 ()) and trinuclear complexes (, R = 1,3,5-(C6H4)3-C6H3; , R = 1,3,5-(C6H4-4-C2C6H4)3-C6H3). In all the complexes the Cu(i) centers are found in a distorted tetrahedral environment that is achieved by tridentate coordination of the ligand and σ-bonding to the alkynyl function. The crystal structures of , and were estimated by single crystal X-ray diffraction analysis. The (31)P, (1)H and (1)H-(1)H COSY NMR spectroscopy confirms that all the molecules remain intact in solution. The photophysical studies carried out in the solid state at 298 and 77 K revealed moderate to weak orange luminescence (Φem up to 19%), tentatively assigned to thermally activated delayed fluorescence for the mononuclear complexes. The quantum yields of emission of demonstrated strong dependence on the nature of the alkynyl ligand, the role of which in the electronic transitions was elucidated by TD-DFT computational studies.