Mono-, di- and trinuclear copper(II) dioxime complexes; 3-{2-[2-(2-hydroxyimino-1-methylpropylideneamino)ethylamino]ethylimino}butan-2-one oxime

A new ligand incorporating a dioxime moiety, 3-{2-[2-(2-hydroxyimino-1-methylpropylideneamino)ethylamino]ethylimino}butan-2-one oxime, (H₂mdo), has been synthesized and its mono-, di- and trinuclear copper(II), and hetero-dinuclear copper(II)–manganese(II) complexes have been prepared and characterized by elemental analyses, magnetic moments, ¹H- and ¹³C-n.m.r., i.r. and mass spectral studies. A mononuclear copper(II) complex of H₂mdo was found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N); the data support the proposed structure of H₂mdo and its complexes.     

Mononuclear metal (II) complexes of a Bis(organoamido)phosphate ligand with antimicrobial activities against Escherichia coli

A new tripodal ligand [PO(NH²MePy)₃] ( L ) (²MePy = 2‐(4‐methyl pyridyl)) have been synthesized by treating phosphorous oxychloride with 2‐Amino‐4‐methylpyridine in toluene under refluxing condition. The ligand was appeared as a white solid and characterized by several standard analytical and spectroscopic techniques such as FT‐IR, NMR (¹H, ¹³C{¹H} and ³¹P{¹H}) and ESI‐MS spectroscopy. The ligand ( L ) undergone metal‐assisted hydrolysis of one P–N bond when treated it with hydrated metal nitrates, M(NO₃)₂·xH₂O (M = Zn, Cu, Co and Ni) under hydrothermal reaction condition in DMF‐H₂O (1:1). This results in the formation of four mononuclear complexes [{PO₂(NH²MePy)₂}₂M] [M = Zn ( 1 ), Cu ( 2 ), Co ( 3 ), Ni ( 4 )], where ligand ( L ) hydrolyses to a anionic bis(organoamido)phosphate, [PO₂(NH²MePy)₂]⁻. All complexes were completely characterized by various analytical techniques and their solid state molecular structures were established by single crystal X‐ray diffraction. All complexes are isostructural with a metal (II) ion situating at the centre of a distorted octahedron. Two tridentate [PO₂(NH²MePy)₂]⁻ ligands are coordinated to metal(II) ion through N‐ and O‐donor atoms, thus neutralizing the charge of the complex. Optical properties of all complexes in solid state have been studied. Moreover, antimicrobial activities of complexes 1 – 4 have been explored. To the best of our knowledge, this is the first report of such compounds investigated for their antimicrobial activities.     

NMR studies on the novel heterobimetallic complexes [M(dppm)(Ph(2)PCH(2)PPh(2)PPPP) {Pt(PPh3)2}]OTf (M = Rh, Ir) derived from the stepwise activation of white phosphorus

The solution structures of the novel heterobimetallic complexes [Ir(dppm)(Ph(2)PCH(2)PPh(2)PPPP){Pt(PPh(3))2}]OTf and [Rh(dppm)(Ph(2)PCH(2)PPh(2)PPPP){Pt(PPh(3))(2)}]OTf derived from the reaction of Rh and Ir--P(5) precursors with [Pt(C2H4)(PPh3)2] have been unambiguously assigned on the basis of 1H NMR and 31P{1H} NMR data. The results are in agreement with the regio-selective insertion of the {Pt(PPh3)2} moiety resulting in a new pentaphosphorus topology which agrees with the formal formation of a unique phosphonium(+)-tetraphosphabutadienide(2-) ligand.     

Synthesis and Structural Studies of 2-(hydroxyimino)-1-methylpropylideneamino-phenyliminobutan-2-one Oxime, Ligand and its Complexes with Cu(II) and Ni(II)

A new ligand incorporating a dioxime moiety, (2E,3E)-3-[(2-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}phenyl)imino]butan-2-one oxime, (H₂Phmdo) (3) has been prepared by reacting 2,3-butanedionemono-{O-[4-(1-methyl-2-oxo-propylideneaminooxy)-2,3-bis-(1-methyl-2-oxo-propylideneaminooxy-methyl)-but-2-enyl]-oxime} (2) with 1,2-phenylenediamine. Mono-, di- and trinuclear copper(II) and/or nickel(II) complexes of H₂Phmdo were characterized by elemental analyses, magnetic moments, ¹H-n.m.r. and ¹³C-n.m.r., i.r. and mass spectral studies. The mononuclear copper(II) and nickel(II) complexes of H₂Phmdo were found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N). In the dinuclear complexes, in which the first Cu^(II) or Ni^(II) ion was complexed with nitrogen atoms of the oxime and imine groups, the second Cu^(II) ion is ligated with dianionic oxygen atoms of the oxime groups and are linked to the 1,10-phenanthroline nitrogen atoms. The data support the proposed structure of H₂Phmdo and its complexes.     

Synthesis,characterization and antioxidant,antibacterial activity Zn2+, Cu2+, Ni2+ and Co2+, complexes of ligand [2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzo[d]imidazole]

New metal complexes of (Zn(II), Co(II), Ni(II) and Cu(II)) based on the ligand 2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzo[d]imidazole] were synthesized, whose structures were determined with the different spectroscopic techniques ¹H NMR,¹³C NMR, FT-IR, UV–Visible and by mass spectrometry. The thermal analysis was performed by TG-DTA. The antioxidant activity of the ligand and its complexes was evaluated by DPPH (2,2-diphenyl-1-picrylhydrazyl) method, in comparison with the synthetic antioxidant, ascorbic acid. The results obtained showed that the antioxidant activity of the ligand and its complexes is moderate and that the copper complex has a high activity that exceeds that of ascorbic acid. Antimicrobial activity of the ligand and its metal complexes was studied against two Gram-positive bacteria: Bacillus subtilis ILP1428B, Staphylococcus aureus CIP543154 and two Gram-negative bacteria: Pseudomonas aeruginosa ATCC27653, Escherichia coli CIP5412 (American Type Culture Collection)the activity data show that the metal complexes are more potent than the free ligand.     

Preparation and structural studies of organotin(IV) complexes formed with organic carboxylic acids

The complexes of six organic carboxylic acids (containing {O,O} donor atoms) with Bu₂Sn(IV)²⁺ and Ph₃Sn(IV)⁺ with ligand to metal ratios of 1 : 1 and 1 : 2, were prepared by two different methods. The FtIR and Raman spectra clearly demonstrated that the organotin(IV) moieties react with the {O,O} atoms of the ligands. It was found that in most cases the -COO^-group was chelated to the central metal ions, but monodentate coordination was also sometimes observed. Complex formation was accompanied by a rearrangement of the hydrogen-bonding network existing in the ligands. The complexes probably have polymeric structures. Comparison of the experimental Mössbauer D values with those calculated on the basis of the point charge model formalism revealed that the organotin(IV) moiety has a trigonal-bipyramidal (tbp) geometry, and in certain cases a tetrahedral (tetr) geometry too. Finally, the local structure of the maleic acid complex formed with Bu₂Sn(IV)²⁺ was determined by an EXAFS method.     

Conformational Rigidity in Complexes [MCl(tBu2PH)3] (M = Rh,Ir)

Reactions of [{M(μ‐Cl)(coe)₂}₂] (M = Rh, Ir; coe = cis‐cyclooctene) with the secondary phosphane tBu₂PH under various molar ratios were investigated. Probably, for kinetic reasons, the reaction behavior of the rhodium species differed from that of the iridium analogue in some instances. During these studies complexes [MCl(tBu₂PH)₃] [M = Rh ( 1 ), Ir ( 2 )] were isolated, and solution variable‐temperature ³¹P{¹H} NMR studies revealed that these complexes show a conformational rigidity on the NMR time scale. Spectra recorded in the temperature range from 173 to 373 K indicated in each case only one rotamer containing three chemically nonequivalent phosphanes due to the restricted rotation of these ligands about the M–P bonds and the tert‐butyl substituents around the P–C(tBu) bonds, respectively. Compound 1 showed in solution already at room temperature in several solvents a dissociation of a phosphane ligand affording the known complex [{Rh(μ‐Cl)(tBu₂PH)₂}₂] beside the free phosphane. In contrast to these findings, the iridium analogue 2 remained completely unchanged under similar conditions and exhibited, therefore, some kinetic inertness. For a better understanding of the NMR spectroscopic investigations, the molecular structure of 1 in the solid state was confirmed by X‐ray crystallography.     

A novel vic-dioxime ligand and its Ni(II), Cu(II) and Co(II) complexes containing calix[4]pyrrole moiety: synthesis, characterization and redox properties

A new calix[4]pyrrole functionalized vic-dioxime, 3-(4-methyl-9,9,14,14,19,19-hexaethylcalix[4]pyrrole)benzoaminoglyoxime (LH₂) was synthesized from anti-chloroglyoxime and 3-aminophenyl-calix[4]pyrrole at room temperature. The mononuclear complexes {nickel(II), copper(II) and cobalt(II)} of this vic-dioxime ligand were prepared and their structures were confirmed by elemental analysis, IR and UV–Vis spectrophotometry, magnetic susceptibility; the MS, ¹H and ¹³C NMR spectra of the LH₂ ligand and its Ni(II) complex were also recorded. The experimental results indicated that the ligand:metal ratio was 2:1 in the cases of Ni(II), Cu(II) and Co(II) complexes as is with most vic-dioximes. Electrochemical properties of the ligand, and its complexes were investigated in DMSO solution by cyclic voltammetry at 200?mV?s^?1 scan rate.     

Synthesis,characterization and in vitro biological activity of cobalt(II), copper(II) and zinc(II) Schiff base complexes derived from salicylaldehyde and D,L‐selenomethionine

New cobalt(II), copper(II) and zinc(II) complexes of Schiff base derived from D,L ‐selenomethionine and salicylaldehyde were synthesized and characterized by elemental analysis, IR, electronic spectra, conductance measurements, magnetic measurements and biological activity. The analytical data showed that the Schiff base ligand acts as tridentate towards divalent metal ions (cobalt, copper, zinc) via the azomethine‐N, carboxylate oxygen and phenolato oxygen by a stoichiometric reaction of M:L (1:1) to form metal complexes [ML(H₂O)], where L is the Schiff base ligand derived from D,L ‐selenomethionine and salicylaldehyde and M = Co(II), Cu(II) and Zn(II). ¹H NMR spectral data of the ligand and Zn(II) complex agree with proposed structures. The conductivity values between 12.87 and 15.63 S cm² mol^?1 in DMF imply the presence of non‐electrolyte species. Antibacterial and antifungal results indicate that the metal complexes are more active than the ligand. Copyright © 2010 John Wiley & Sons, Ltd.     

Solid-state NMR on thermal and fire residues of bisphenol A polycarbonate/silicone acrylate rubber/bisphenol A bis(diphenyl-phosphate)/(PC/SiR/BDP) and PC/SiR/BDP/zinc borate (PC/SiR/BDP/ZnB) - Part I: PC charring and the impact of BDP and ZnB

Structural changes in the condensed phase of bisphenol A polycarbonate (containing 0.45 wt% poly(tetrafluoroethylene))/silicone acrylate rubber/bisphenol A bis(diphenyl-phosphate) (PC/SiR/BDP) and PC/SiR/BDP/zinc borate (PC/SiR/BDP/ZnB) during thermal treatment in nitrogen atmosphere and in fire residues were investigated by solid-state NMR. ¹H, ¹¹B, ¹³C and ³¹P NMR experiments using direct excitation with a single pulse and ¹H-³¹P cross-polarization (CP) were carried out including ³¹P{¹H} and ¹³C{³¹P}double-resonance techniques (REDOR: Rotational Echo Double Resonance) on a series of heat-treated samples (580 K-850 K). Because many amorphous phases occur in the solid residues, and solid-state NMR spectroscopy addresses the most important sites carbon, phosphorus and boron, this paper is the key analytical approach for understanding the pyrolysis and flame retarding phenomenon in the condensed phase of PC/SiR/BDP and PC/SiR/BDP/ZnB.For the system PC/SiR/BDP it is shown that (i) at temperatures around 750-770 K (main decomposition step) carbonaceous charring of PC occurs and arylphosphate structures are still present, reacted in part with the decomposing PC; (ii) for higher temperatures from 770 K the phosphorus remaining in the solid phase increasingly converts to amorphous phosphonates and inorganic orthophosphates with a minor amount of crystalline orthophosphates; and (iii) ¹H-³¹P{¹H} CP REDOR and ¹H-¹³C{³¹P} CP REDOR NMR experiments suggest that the phosphates and phosphonates are bound via oxygen to aromatic carbons, indicating the interaction with the carbonaceous char.When ZnB is added to the system PC/SiR/BDP, (i) ZnB leads to a slightly enhanced PC decomposition for temperatures below 750 K; (ii) α-Zn₃(PO₄)₂ and borophosphate (BPO₄) are formed in small amounts at high temperatures suggesting a reaction between BDP and ZnB during thermal decomposition; and (iii) most of the borate remains in the solid residues, forming an amorphous pure borate network, with the BO₃/BO₄ ratio increasing with higher temperatures.The NMR data of thermal and fire residues are highly correlated, underlining the importance of this work for understanding the pyrolysis and flame retardancy mechanisms in the condensed phase during the burning of the PC/SiR blends.     

Fluxional behaviour of Rh4(CO)8{P(OPh)3}4: A 13C-{31P, 1H} NMR study

Variable temperature ¹³C-{³¹P, ¹H} NMR studies on Rh₄(CO)₈ {P(OPh)₃}₄ show that the solid state structure is maintained in solution at low temperature; at higher temperatures carbonyl migration occurs around the metal polyhedron with the lowest energy migration occurring via a Cotton type mechanism which also involves a rocking motion about the unique rhodium in the basal plane. At +82°C, the fast exchange limiting ¹³C-{³¹P, ¹H} and ³¹P spectra exhibit a quintet and doublet of quartets, respectively.     

Stereoisomerism of Octahedral Titanium <Emphasis Type="Italic">cis</Emphasis>-Tetrafluoro Complexes with Ph<Subscript>2</Subscript>P(O)CH<Subscript>2</Subscript>CH(OH)Me Enantiomers According to <Superscript>19</Superscript>F NMR Data

Effect of enantiomers of a monodentate ligand on the stereoisomerism of mixed octahedral cis-tetrafluoro complexes of d⁰ transition metals has been studied by ¹⁹F{¹H} and ³¹P{¹H} NMR by the example of TiF₄ complexation in CH₂Cl₂ with Ph₂P(O)CH₂CH(OH)Me (L) containing asymmetric carbon atom in the aliphatic hydrocarbon group that constitutes a racemic mixture of enantiomers. Composition of complexes formed in solution has been determined, conclusion has been drawn on the relative stereochemical configuration of the chiral and meso stereoisomers of octahedral complex cis-TiF₄L₂ on the basis of analysis of ¹⁹F NMR spectra, using the heterotropism concept.     

Organotin(IV) complexes of polyhydroxyalkyl carboxylic acids and some related ligands

A number of dibutyltin(IV) complexes of polyhydroxyalkyl carboxylic acids (O donor atoms) and amino acids (O,N donor atoms) were prepared in the solid state. The binding sites of the ligands were determined by means of FT-IR, Raman and ¹³C NMR spectroscopy. Partial quadrupole splitting calculations were utilized to determine the coordination geometry around the Sn(IV) centre by means of Mössbauer measurements. The results showed that in the solid state oligomeric complexes are formed, with the -COO^- groups as bridges between the organometallic cations. The {Sn} atoms are mostly in trigonal bipyramidal surroundings. The Sn-O and Sn-C bond distances were determined by EXAFS measurements to be 207-234 and 295 pm, respectively. Evaluation of the pH-metric and NMR titration curves in Me₂Sn(IV)-D-gluconic acid system revealed that the equilibria in aqueous solution are fairly complicated. In acidic solution, the formation of 1 : 1 and 1 : 2 -COO^- coordinated species predominate, but deprotonation of the alcoholic -OH groups also starts at very low pH. In the pH range 5-9, NMR provides experimental evidence of ligand-exchange reactions without pH-metrically detectable proton release. In alkaline solution, further deprotonation processes occur, resulting in either alkoxo or mixed hydroxo complexes. The carboxylate coordination is expected for the amino acid ligands but the shift of the νN-H stretching vibrations in the FT-IR spectra demonstrated that the ammine group also binds to the metal ion in the solid Bu₂Sn(IV)complexes.     

Synthesis and structural studies of (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}pyridin-2-yl)imino]butan-2-one oxime, ligand and its mono-, di- and trinuclear copper(II) complexes

A new dioxime ligand, (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}-pyridin-2-yl)imino]butan-2-one oxime, (H₂Pymdo) (3) has been synthesized in H₂O by reacting 2,3-butenedione monoxime (2) with 2,6-diaminopyridine. Mono-, di- and tri-nuclear copper(II) complexes of the dioxime ligand (H₂Pymdo) and/or 1,10-phenanthroline have been prepared. The dioxime ligand (H₂Pymdo) and its copper(II) complexes were characterized by ¹H-n.m.r., ¹³C-n.m.r. and elemental analyses, magnetic moments, i.r. and mass spectral studies. The mononuclear copper(II) complex of H₂Pymdo was found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N). In the dinuclear complexes, in which the first Cu(II) ion was complexed with nitrogen atoms of the oxime and imine groups, the second Cu(II) ion is ligated with dianionic oxygen atoms of the oxime groups and are linked to the 1,10-phenanthroline nitrogen atoms. The trinuclear copper(II) complex (6) was formed by coordination of the third Cu(II) ion with dianionic oxygen atoms of each of two molecules of the mononuclear copper(II) complexes. The data support the proposed structure of H₂Pymdo and its Cu(II) complexes.     

Synthesis and characterization of heterocyclic Schiff base and its complexes with Cu(II), Ni(II), Co(II), Zn(II), and Cd(II)

A new Schiff base, {1-[(2-hydroxy-naphthalen-1-ylmethylene)-amino]-4-phenyl-2-thioxo-1, 2-dihydro-pyrimidin-5-yl}-phenyl-methanone, has been synthesized from N-amino pyrimidine-2-thione and 2-hydroxynaphthaldehyde. Metal complexes of the Schiff base were prepared from acetate/chloride salts of Cu(II), Co(II), Ni(II), Zn(II), and Cd(II) in methanol. The chemical structures of the Schiff-base ligand and its metal complexes were confirmed by elemental analyses, IR, ¹³C-NMR, ¹H-NMR, API-ES, UV-Visible spectroscopy, magnetic susceptibility, and thermogravimetric analyses. The electronic spectral data and magnetic moment measurements suggest mononuclear octahedral and mononuclear or binuclear square planar structures for the metal complexes. In light of these results, it was suggested that this ligand coordinates to each metal atom by hydroxyl oxygen, azomethine nitrogen, and thione sulfur to form octahedral complexes with Cd(II) and Zn(II).     

Synthesis and spectroscopic characterization of indomethacin-Cd(II), Ce(III), and Th(IV) complexes: IR, 1H NMR,thermal, and biological studies

Solid complexes have been prepared and characterized by IR, UV-Vis, elemental analysis, and ¹H NMR. Indomethacin forms complexes with Cd(II), Ce(III), and Th(IV) ions in molar ratios (ligand: metal) (2: 1), (3: 1), and (4: 1), respectively. The IR spectra of the complexes suggest that the Indomethacin behaves as a monobasic monodentate ligand coordinated to the metal ions via the deprotonated carboxylate group. Prepared complexes exhibit higher antimicrobial activity against several microorganisms, compared to free ligand.     

Preparation and structural studies on dibutyltin(IV) complexes with pyridine mono- and dicarboxylic acids

A number of organotin(IV) complexes with pyridine mono- and dicarboxylic acids (containing ligating -COOH group(s) and aromatic {N} atoms) were prepared in the solid state. The bonding sites of the ligands were determined by means of FT-IR spectroscopic measurements. It was found that in most cases the -COO⁻ groups form bridges between two central {Sn} atoms, thereby leading to polymeric (oligomeric) complexes. On this basis, the experimental ¹¹⁹Sn Mössbauer spectroscopic data were treated with partial quadrupole splitting approximations. The calculations predicted the existence of complexes with octahedral (oh) and trigonal-bipyramidal (tbp) structures, but the formation of complexes with pentagonal-bipyramidal (pbp) structures could not be ruled out. Single-crystals of 2-picolinic and pyridine-2,6-dicarboxylic acid Bu₂Sn(IV)²⁺ complexes were obtained. The X-ray diffraction studies revealed that the central {Sn} atoms are in a pbp environment with bond distances characteristic of organotin(IV) compounds. The two butyl groups are located in axial positions. ¹¹⁹Sn NMR measurements in dmso solution and in the solid state indicated that the polymeric structures of the complexes are not retained in solution. The results of the solid-state ¹¹⁹Sn NMR measurements for compounds 1a, 2a and 6a are in agreement with the structures predicted by Mössbauer spectroscopy and revealed by X-ray diffraction.     

Coordination chemistry of 2,6-bis(diphenylphosphorylmethyl)-4-methylphenol

The trifunctional ligand, 2,6-bis(diphenylphosphorylmethyl)-4-methylphenol (L ₂), forms complexes with cerium(III) nitrate having a ligand to metal ratio of 1: 1, 2: 1, and 3: 1. The structures of these complexes in the solid state and in solution were studied by X-ray diffraction, IR and NMR (¹H and ³¹P) spectroscopy, and conformational analysis (molecular mechanics). The 2: 1 complexes of L ₂ with lanthanum(III) and neodymium(III) nitrates were synthesized and characterized. In all complexes, the neutral ligand is coordinated through both phosphoryl oxygen atoms. The hydroxy oxygen atom is coordinated only in some complexes, and the hydrogen atom of the hydroxy group is involved in hydrogen bonding. The compositions and structures of the resulting complexes depend on the method of synthesis and the nature of solvent. The ligand was found to undergo easy inner-sphere oxidation. The structure of one of the transformation products was established by X-ray diffraction. Unlike the coordinated ligand, the free ligand is very stable to oxidation. Dedicated to Corresponding Member of the Russian Academy of Sciences T. A. Mastryukova. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2440–2454, November, 2005.     

Bis -(3,5-dimethyl-pyrazolyl-1-methyl)-(3-phosphanyl-propyl)-amine complexes of copper(II), nickel(II), and cobalt(II)

A series of Cu(II), Co(II), and Ni(II) complexes of bis-(3,5-dimethyl-pyrazolyl-1-methyl)-(3-phosphanyl-propyl)-amine C₁₅H₂₆N₅P (1), prepared from 3-aminopropylphosphine and 1-hydroxymethyl-3,5-dimethylpyrazole were characterized. The nature of bonding and the geometry of the complexes have been deduced from elemental analysis, infrared, electronic, ¹H NMR, ³¹P NMR spectra, magnetic susceptibility, and conductivity measurements. The studies indicate octahedral geometry for nickel complex and square pyramidal geometry for copper and cobalt complexes. The EPR spectra of copper complex in acetonitrile at 300 K and 77 K were recorded. Biological activities of the ligand and metal complexes have been studied on Staphylococcus aureus, Escherichia coli, Aspergillus niger, and Aspergillus flavus by well-diffusion method. The zone of inhibition values were measured at 37°C for a period of 24 h. The electrochemical behavior of copper complexes was studied by cyclic voltammetry. Catalytic study indicates the copper complex has efficient catalytic activity in oxidation of amitriptyline.     

Neutral gold(I) metallosupramolecular compounds: synthesis and characterization, photophysical properties, and density functional theory studies

The reaction of the tris-indole InTREN ligand (L) with different gold phosphine fragments allows the construction of new gold(I) complexes with different geometries depending on the chosen phosphine. A metallodendrimeric structure is obtained when the gold atom is linked to a triphenylphosphine ligand, and neutral gold(I) metallocryptands are constructed when a triphosphine is used. Characterization of the compounds was accomplished by 31P{1H} and 1H NMR, IR, absorption, and fluorescence spectroscopies, electrospray ionization mass spectrometry (ESI-MS(+)), and elemental analysis, and their geometry was optimized using density functional theory (B3LYP). Time-dependent density functional theory (TD-DFT) calculations have been used to assign the lowest energy absorption bands to LMCT N(p, tertiary amine)-->Au transitions. Photophysical characterization of the complexes shows strong luminescence in the solid state. The formation of heterobimetallic species has been detected in solution in the presence of equimolar quantities of metal cations, and their structures have been identified by a combination of spectroscopic methods and mass spectrometry.