Three-atom-wide gold quantum rods with periodic elongation and strongly polarized excitons.

Atomically precise control over anisotropic nanoclusters constitutes a grand challenge in nanoscience. In this work, we report our success in achieving a periodic series of atomically precise gold quantum rods (abbrev. Au QRs) with unusual excitonic properties. These QRs possess hexagonal close-packed kernels with a constant three-atom diameter but increasing aspect ratios (ARs) from 6.3 to 18.7, all being protected by the same thiolate (SR) ligand. The kernels of the QRs are in a Au1-(Au3)n-Au1 configuration (where n is the number of Au3 layers) and follow a periodic elongation with a uniform Au18(SR)12 increment consisting of four Au3 layers. These Au QRs possess distinct HOMO-LUMO gaps (Eg = 0.6 to 1.3 eV) and exhibit strongly polarized excitonic transition along the longitudinal direction, resulting in very intense absorption in the near-infrared (800 to 1,700 nm). While excitons in gapped systems and plasmons in gapless systems are distinctly different types of excitations, the strongly polarized excitons in Au QRs surprisingly exhibit plasmon-like behaviors manifested in the shape-induced polarization, very intense absorption (~106 M-1 cm-1), and linear scaling relations with the AR, all of which resemble the behaviors of conventional metallic-state Au nanorods (i.e., gapless systems), but the QRs possess distinct gaps and very long excited-state lifetimes (10 to 2,122 ns), which hold promise in applications such as near-infrared solar energy utilization, hot carrier generation and transfer. The observation of plasmon-like behaviors from single-electron transitions in Au QRs elegantly bridges the distinct realms of single-electron and collective-electron excitations and may stimulate more research on excitonics and plasmonics.

Direct Observation of the Pressure-Induced Structural Variation in Gold Nanoclusters and the Correlated Optical Response.

The ability to gradually modify the atomic structures of nanomaterials and directly identify such structural variation is important in nanoscience research. Here, we present the first example of a high-pressure single-crystal X-ray diffraction analysis of atomically precise metal nanoclusters. The pressure-dependent, subangstrom structural evolution of an ultrasmall gold nanoparticle, Au25S18, has been directly identified. We found that a 0.1 Å decrease of the Au-Au bond length could induce a blue-shift of 30 nm in the photoluminescence spectra of gold nanoclusters. From theoretical calculations, the origins of the blue-shift and enhanced photoluminescence under pressure are investigated, which are ascribed to molecular orbital symmetry and conformational locking, respectively. The combination of the high-pressure in situ X-ray results with both theoretical and experimental optical spectra provides a direct and generalizable avenue to unveil the underlying structure-property relations for nanoclusters and nanoparticles which cannot be obtained through traditional physical chemistry measurements.

Anomalous Structural Transformation of Cu(I) Clusters into Multifunctional CuAg Nanoclusters.

We report an anomalous structural transformation of a Cu(I) cluster into two different types of copper-silver (CuAg) alloy nanoclusters. Different from previous reports, we demonstrate that under specifically designed reaction conditions, the Ag-doping could induce a substantial growth of the starting Cu15 and a Ag13Cu20 nanocluster was obtained via the unexpected insertion of an Ag13 kernel inside the Cu(I)-S shell. Ag13Cu20 demonstrates high activity to initiate the photopolymerization of previously hard-to-print inorganic polymers in 3D laser microprinting. Interestingly, a slight modification of the reaction condition leads to the formation of another Ag18-xCuxS (8≤x) nanocluster templated by a central S2- anion, which possesses a unique electronic structure compared to conventional template-free CuAg nanoclusters. Overall, this work unveils the intriguing doping chemistry of Cu clusters, as well as their capability to create different types of alloy nanoclusters with previously unobtainable structures and multifunctionality.

Tailoring Carbon Tails of Ligands on Au52(SR)32 Nanoclusters Enhances the Near-Infrared Photoluminescence Quantum Yield from 3.8 to 18.3.

One of the important factors that determine the photoluminescence (PL) properties of gold nanoclusters pertain to the surface. In this study, four Au52(SR)32 nanoclusters that feature a series of aromatic thiolate ligands (-SR) with different bulkiness at the para-position are synthesized and investigated. The near-infrared (NIR) photoluminescence (peaks at 900-940 nm) quantum yield (QY) is largely enhanced with a decrease in the ligand's para-bulkiness. Specifically, the Au52(SR)32 capped with the least bulky p-methylbenzenethiolate (p-MBT) exhibits the highest PLQY (18.3% at room temperature in non-degassed dichloromethane), while Au52 with the bulkiest tert-butylbenzenethiolate (TBBT) only gives 3.8%. The large enhancement of QY with fewer methyl groups on the ligands implies a nonradiative decay via the multiphonon process mediated by C-H bonds. Furthermore, single-crystal X-ray diffraction (SCXRD) comparison of Au52(p-MBT)32 and Au52(TBBT)32 reveals that fewer methyl groups at the para-position lead to a stronger interligand π···π stacking on the Au52 core, thus restricting ligand vibrations and rotations. The emission nature is identified to be phosphorescence and thermally activated delayed fluorescence (TADF) based on the PL lifetime, 3O2 quenching, and temperature-dependent PL and absorption studies. The 1O2 generation efficiencies for the four Au52(SR)32 NCs follow the same trend as the observed PL performance. Overall, the highly NIR-luminescent Au52(p-MBT)32 nanocluster and the revealed mechanisms are expected to find future applications.

Ultrastable silver nanoparticles.

Noble-metal nanoparticles have had a substantial impact across a diverse range of fields, including catalysis, sensing, photochemistry, optoelectronics, energy conversion and medicine. Although silver has very desirable physical properties, good relative abundance and low cost, gold nanoparticles have been widely favoured owing to their proved stability and ease of use. Unlike gold, silver is notorious for its susceptibility to oxidation (tarnishing), which has limited the development of important silver-based nanomaterials. Despite two decades of synthetic efforts, silver nanoparticles that are inert or have long-term stability remain unrealized. Here we report a simple synthetic protocol for producing ultrastable silver nanoparticles, yielding a single-sized molecular product in very large quantities with quantitative yield and without the need for size sorting. The stability, purity and yield are substantially better than those for other metal nanoparticles, including gold, owing to an effective stabilization mechanism. The particular size and stoichiometry of the product were found to be insensitive to variations in synthesis parameters. The chemical stability and structural, electronic and optical properties can be understood using first-principles electronic structure theory based on an experimental single-crystal X-ray structure. Although several structures have been determined for protected gold nanoclusters, none has been reported so far for silver nanoparticles. The total structure of a thiolate-protected silver nanocluster reported here uncovers the unique structure of the silver thiolate protecting layer, consisting of Ag2S5 capping structures. The outstanding stability of the nanoparticle is attributed to a closed-shell 18-electron configuration with a large energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, an ultrastable 32-silver-atom excavated-dodecahedral core consisting of a hollow 12-silver-atom icosahedron encapsulated by a 20-silver-atom dodecahedron, and the choice of protective coordinating ligands. The straightforward synthesis of large quantities of pure molecular product promises to make this class of materials widely available for further research and technology development.

Sharp Transition from Nonmetallic Au246 to Metallic Au279 with Nascent Surface Plasmon Resonance.

The optical properties of metal nanoparticles have attracted wide interest. Recent progress in controlling nanoparticles with atomic precision (often called nanoclusters) provide new opportunities for investigating many fundamental questions, such as the transition from excitonic to plasmonic state, which is a central question in metal nanoparticle research because it provides insights into the origin of surface plasmon resonance (SPR) as well as the formation of metallic bond. However, this question still remains elusive because of the extreme difficulty in preparing atomically precise nanoparticles larger than 2 nm. Here we report the synthesis and optical properties of an atomically precise Au279(SR)84 nanocluster. Femtosecond transient absorption spectroscopic analysis reveals that the Au279 nanocluster shows a laser power dependence in its excited state lifetime, indicating metallic state of the particle, in contrast with the nonmetallic electronic structure of the Au246(SR)80 nanocluster. Steady-state absorption spectra reveal that the nascent plasmon band of Au279 at 506 nm shows no peak shift even down to 60 K, consistent with plasmon behavior. The sharp transition from nonmetallic Au246 to metallic Au279 is surprising and will stimulate future theoretical work on the transition and many other relevant issues.

Reconstructing the Surface of Gold Nanoclusters by Cadmium Doping.

Atomically precise metal nanoclusters with tailored surface structures are important for both fundamental studies and practical applications. The development of new methods for tailoring the surface structure in a controllable manner has long been sought. In this work, we report surface reconstruction induced by cadmium doping into the [Au23(SR)16]- (R = cyclohexyl) nanocluster, in which two neighboring surface Au atomic sites "coalesce" into one Cd atomic site and, accordingly, a new bimetal nanocluster, [Au19Cd2(SR)16]-, is produced. Interestingly, a Cd(S-Au-S)3 "paw-like" surface motif is observed for the first time in nanocluster structures. In such a motif, the Cd atom acts as a junction which connects three monomeric -S-Au-S- motifs. Density functional theory calculations are performed to understand the two unique Cd locations. Furthermore, we demonstrate different doping modes when the [Au23(SR)16]- nanocluster is doped with different metals (Cu, Ag), including (i) simple substitution and (ii) total structure transformation, as opposed to surface reconstruction for Cd doping. This work greatly expands doping chemistry for tailoring the structures of nanoclusters and is expected to open new avenues for designing nanoclusters with novel surface structures using different dopants.

Gold Quantum Boxes: On the Periodicities and the Quantum Confinement in the Au28, Au36, Au44 , and Au52 Magic Series.

Revealing the size-dependent periodicities (including formula, growth pattern, and property evolution) is an important task in metal nanocluster research. However, investigation on this major issue has been complicated, as the size change is often accompanied by a structural change. Herein, with the successful determination of the Au44(TBBT)28 structure, where TBBT = 4-tert-butylbenzenethiolate, the missing size in the family of Au28(TBBT)20, Au36(TBBT)24, and Au52(TBBT)32 nanoclusters is filled, and a neat "magic series" with a unified formula of Au8n+4(TBBT)4n+8 (n = 3-6) is identified. Such a periodicity in magic numbers is a reflection of the uniform anisotropic growth patterns in this magic series, and the n value is correlated with the number of (001) layers in the face-centered cubic lattice. The size-dependent quantum confinement nature of this magic series is further understood by empirical scaling law, classical "particle in a box" model, and the density functional theory calculations.

Crystal Structure of Barrel-Shaped Chiral Au130(p-MBT)50 Nanocluster.

We report the structure determination of a large gold nanocluster formulated as Au130(p-MBT)50, where p-MBT is 4-methylbenzenethiolate. The nanocluster is constructed in a four-shell manner, with 55 gold atoms assembled into a two-shell Ino decahedron. The surface is protected exclusively by -S-Au-S- staple motifs, which self-organize into five ripple-like stripes on the surface of the barrel-shaped Au105 kernel. The Au130(p-MBT)50 can be viewed as an elongated version of the Au102(SR)44. Comparison of the Au130(p-MBT)50 structure with the recently discovered icosahedral Au133(p-TBBT)52 nanocluster (where p-TBBT = 4-tert-butylbenzenethiolate) reveals an interesting phenomenon that a subtle ligand effect in the para-position of benzenethiolate can significantly affect the gold atom packing structure, i.e. from the 5-fold twinned Au55 decahedron to 20-fold twinned Au55 icosahedron.

Physician communication in the operating room.

In this study, communication research was conducted with multidisciplinary groups of operating-room physicians. Theoretical frameworks from intercultural communication and rhetoric were used to (a) measure latent cultural communication variables and (b) conduct communication training with the physicians. A six-step protocol guided the research with teams of physicians from different surgical specialties: anesthesiologists, general surgeons, and obstetrician-gynecologists (n = 85). Latent cultural communication variables were measured by surveys administered to physicians before and after completion of the protocol. The centerpiece of the 2-hour research protocol was an instructional session that informed the surgical physicians about rhetorical choices that support participatory communication. Post-training results demonstrated scores increased on communication variables that contribute to collaborative communication and teamwork among the physicians. This study expands health communication research through application of combined intercultural and rhetorical frameworks, and establishes new ways communication theory can contribute to medical education.

Bio-Based Bisfuran: Synthesis, Crystal Structure and Low Molecular Weight Amorphous Polyester.

Discovery of renewable monomer feedstocks for fabrication of polymeric demand is critical in achieving sustainable materials. In the present work we have synthesized bisfuran diol (BFD) monomer from furfural, over four steps. BFD was examined via X-ray crystallography to understand the molecular arrangement in space, hydrogen bonding and packing of the molecules. This data was further used to compare BFD with structurally related Bisphenol A (BPA), and its known derivatives to predict the potential estrogenic or anti-estrogenic activities in BFD. Further, BFD was reacted with succinic acid to generate polyester material, bisfuran polyester (BFPE-1). MALDI characterization of BFPE-1 indicates low molecular weight polyester and thermal analysis reveals amorphous nature of the material.

Au36(SR)22 Nanocluster and a Periodic Pattern from Six to Fourteen Free Electrons in Core Size Evolution.

An Au36(S-tBu)22 nanocluster (NC) is synthesized using the bulky tert-butyl thiol as the ligand. Single-crystal X-ray crystallography reveals that it has an Au25 core which evolves from the Au22 core in the previously reported Au30(S-tBu)18, and the Au25 core is protected by longer staple-like surface motifs. The new Au36 NC extends the members of the face-centered cubic structural evolution by adding an Au3 triangle and an Au4 tetrahedron unit. Additionally, it is found that Au36 emits near-infrared photoluminescence at 863 nm with a quantum yield (QY) of 4.3%, which is five times larger than that of Au30(S-tBu)18-the closest neighbor in the structural evolution pattern. The higher QY of Au36 is attributed to a larger radiative relaxation (kr), resulting from the structural effect. Finally, we find that the longer staple motifs lead to enhanced stability of Au36(S-tBu)22 relative to Au30(S-tBu)18.

Electron paramagnetic resonance spectroscopic study of copper hopping in doped bis(L-histidinato)cadmium dihydrate.

Electron paramagnetic resonance (EPR) spectroscopy was used to study Cu(II) dynamic behavior in a doped biological model crystal, bis(L-histidinato)cadmium dihydrate, in order to gain better insight into copper site stability in metalloproteins. Temperature-dependent changes in the low temperature X-band EPR spectra became visible around 100 K and continued up to room temperature. The measured 298 K g-tensor (principal values: 2.17, 2.16, 2.07) and copper hyperfine coupling tensor (principal values: -260, -190, -37 MHz) were similar to the average of the 77 K tensor values pertaining to two neighboring histidine binding sites. The observed temperature dependence was interpreted using Anderson's theory of motional narrowing, where the magnetic parameters for the different states are averaged as the copper rapidly hops between sites. The EPR pattern was also found to undergo a sharp sigmoidal-shaped, temperature-dependent conversion between two species with a critical temperature T(c) ≈ 160 K. The species below T(c) hops between the two low temperature site patterns, and the one above T(c) represents an average of the molecular spin Hamiltonian coupling tensors of the two 77 K sites. In addition, the low and high temperature species hop between one another, contributing to the dynamic averaging. Spectral simulations using this 4-state model determined a hop rate between the two low temperature sites ν(h4) = 4.5 × 10(8) s(-1) and between the low and high temperature states ν(h2) = 1.7 × 10(8) s(-1) at 160 K. An Arrhenius relationship of hop rate and temperature gave energy barriers of ΔE4 = 389 cm(-1) and ΔE2 = 656 cm(-1) between the two low temperature sites and between the low and high temperature states, respectively.

A series of N-(2-phenylethyl)nitroaniline derivatives as precursors for slow and sustained nitric oxide release agents.

2,4-Dinitro-N-(2-phenylethyl)aniline, C14H13N3O4, (I), crystallizes with one independent molecule in the asymmetric unit. The adjacent amine and nitro groups form an intramolecular N-H...O hydrogen bond. The anti conformation about the ethyl C-C bond leads to the phenyl and aniline rings being essentially parallel. Molecules are linked into dimers by intermolecular N-H...O hydrogen bonds, such that each amine H atom participates in a three-centre interaction with two nitro O atoms. Though the dimers pack so that the arene rings of adjacent molecules are parallel, the rings are staggered and π-π interactions do not appear to be favoured. 4,6-Dinitro-N,N'-bis(2-phenylethyl)benzene-1,3-diamine, C22H22N4O4, (II), differs from (I) in the presence of a second 2-phenylethylamine group on the substituted ring. Compound (II) also crystallizes with one unique molecule in the asymmetric unit. Both amine groups are involved in intramolecular N-H...O hydrogen bonds with adjacent nitro groups. Although one ethyl group adopts an anti conformation as in (I), the other is gauche, with the result that the pendant phenyl rings are not parallel. The amine group that is part of the gauche conformation participates in a three-centre N-H...O hydrogen bond with the nitro group of a neighbouring molecule, leading to dimers as in (I). The other amine H atom does not form any intermolecular hydrogen bonds. The packing leads to separations of ca 3.4 Šof the parallel anti phenyl and aminobenzene rings. 2-Cyano-4-nitro-N-(2-phenylethyl)aniline, C15H13N3O2, (III), differs from (I) only in having a cyano group in place of the 2-nitro group. The absence of the adjacent nitro group eliminates the intramolecular N-H...O hydrogen bond. Molecules of (III) adopt the same anti conformation about the ethyl group as in (I), but crystallize in the higher-symmetry monoclinic space group P21/n. The molecules are linked into dimers via N-H...N amine-cyano hydrogen bonds, while the nitro groups are not involved in any N-H...O interactions. Owing to the different symmetry, the molecules pack in a herringbone pattern with fewer face-to-face interactions between the rings. The closest such interactions are about 3.5 Šbetween rings that are largely slipped past one another. 4-Methylsulfonyl-2-nitro-N-(2-phenylethyl)aniline, C15H16N2O4S, (IV), differs from (I) in having a methylsulfonyl group in place of the 4-nitro group. The intramolecular N-H...O hydrogen bond is present as in (I). However, unlike (I), the conformation about the ethyl group is gauche, so the two arene rings are nearly perpendicular rather than parallel. The packing is significantly different from the other three structures in that there are no intermolecular hydrogen bonds involving the N-H groups. The molecules are arranged in tetragonal columns running along the c axis, with the aniline rings mostly parallel and separated by ca 3.7 Å. Taken together, these structures demonstrate that modest changes in functional groups cause significant differences in molecular conformation, intermolecular interactions and packing.

Improved climate, culture, and communication through multidisciplinary training and instruction.

OBJECTIVE: The objective of the study was to determine the effectiveness of multidisciplinary team training on organizational culture and team communication. STUDY DESIGN: The training included a 6-step protocol: (1) a pretest survey assessing cultural attitudes and perceptions, (2) a baseline high-fidelity simulation session, (3) invitational medical rhetoric instruction, (4) a second high-fidelity simulation session, (5) a posttest survey assessing changed cultural attitudes and perceptions, and (6) a debriefing with participants. Teams of 4 physicians trained together: 2 obstetricians and 2 anesthesiologists. Forty-four physicians completed the training protocol during 2010 and 2011. RESULTS: Paired-sample t tests demonstrated significant decreases in autonomous cultural attitudes and perceptions (t = 8.23, P < .001) and significant increases in teamwork cultural attitudes and perceptions (t = -4.05, P < .001). Paired-sample t tests also demonstrated significant increases in communication climate that invited participation and integrated information from both medical services (t = -5.80, P < .001). CONCLUSION: The multidisciplinary team training program specified in this report resulted in increased teamwork among obstetricians and anesthesiologists.

Synthesis and calorimetric, spectroscopic, and structural characterization of isocyanide complexes of trialkylaluminum and tri-tert-butylgallium.

Addition of tert-butylisocyanide or 2,6-dimethylphenylisocyanide to a solution of trialkylaluminum or trialkylgallium results in formation of complexes R(3)M·C≡N(t)Bu (M = Al, R = Me (1), Et (2), (i)Bu (3), (t)Bu (4); M = Ga, R = (t)Bu (9)) or R(3)M·C≡N(2,6-Me(2)C(6)H(3)) (M = Al, R = Me (5), Et (6), (i)Bu (7), (t)Bu (8); M = Ga, R = (t)Bu (10)), respectively. Complexes 1, 4, 5, and 8-10 are isolated as solids, whereas the triethylaluminum and triisobutylaluminum adducts 2, 3, 6, and 7 are viscous oils. Complexes 1-10 were characterized by NMR ((1)H, (13)C) and IR spectroscopies, and the molecular structures of 4, 5, and 8-10 were also determined by X-ray crystallography. The frequency of the C≡N stretch of the isocyanide increased by 58-91 cm(-1) upon complexation, consistent with coordination of the isocyanide as a σ donor. Enthalpies of complex formation for 1-10 were determined by isothermal titration calorimetry. Enthalpy data suggest the following order of decreasing Lewis acidity: (t)Bu(3)Al ≫ (i)Bu(3)Al ≥ Me(3)Al ≈ Et(3)Al ≫ (t)Bu(3)Ga. In the absence of oxygen and protic reagents, the reported complexes do not undergo insertion or elimination reactions upon heating their benzene-d(6) solutions to 80 °C.

Physician communication in the operating room: expanding application of face-negotiation theory to the health communication context.

Communication variables that are associated with face-negotiation theory were examined in a sample of operating-room physicians. A survey was administered to anesthesiologists and surgeons at a teaching hospital in the southwestern United States to measure three variables commonly associated with face-negotiation theory: conflict-management style, face concern, and self-construal. The survey instrument that was administered to physicians includes items that measured these three variables in previous face-negotiation research with slight modification of item wording for relevance in the medical setting. The physician data were analyzed using confirmatory factor analysis, Pearson's correlations, and t-tests. Results of this initial investigation showed that variables associated with face-negotiation theory were evident in the sample physician population. In addition, the correlations were similar among variables in the medical sample as those found in previous face-negotiation research. Finally, t-tests suggest variance between anesthesiologists and surgeons on specific communication variables. These findings suggest three implications that warrant further investigation with expanded sample size: (1) An intercultural communication theory and instrument can be utilized for health communication research; (2) as applied in a medical context, face-negotiation theory can be expanded beyond traditional intercultural communication boundaries; and (3) theoretically based communication structures applied in a medical context could help explain physician miscommunication in the operating room to assist future design of communication training programs for operating-room physicians.

Quantification of CH···π interactions: implications on how substituent effects influence aromatic interactions.

Attractive interactions between a substituted benzene ring and an α-substituted acetate group were determined experimentally by using the triptycene model system. The attractive interaction correlates well with the Hammett constants σ(m) (R(2)=0.90), but correlates much better with the acidity of the α-protons (R(2)=0.98).

Gold-catalyzed transannular [4+3] cycloaddition reactions.

Macrocyclic propargyl acetates containing a furan ring were prepared by using a CrCl(2)-promoted reaction. In the presence of either a Au(I) or Au(III) catalyst, a tandem 3,3-rearrangement/transannular [4+3] cycloaddition reaction occurred to give propargyl acetates that are regio- and diastereospecific. The regiochemistry of the product is controlled by the position of the acetoxy group in the starting material and the stereochemistry of the reaction depends on the ring size.

Luminescent low-valent rhenium complexes with 1,2-bis(dialkylphosphino)ethane ligands. synthesis and X-ray crystallographic, electrochemical, and spectroscopic characterization.

A series of low-valent rhenium phosphine complexes with the general formula [Re(dmpe)(3-x)(depe)(x)](2+/+) (x = 0-3), where dmpe is 1,2-bis(dimethylphosphino)ethane and depe is 1,2-bis(diethylphosphino)ethane, were synthesized and characterized. The reaction of [Re(benzil)(PPh(3))Cl(3)] with the appropriate phosphine yielded the homoleptic tris complexes [Re(dmpe)(3)](+) and [Re(depe)(3)](2+), while the mixed-ligand complexes [Re(dmpe)(2)(depe)](+) and [Re(dmpe)(depe)(2)](2+) were prepared from [Re(dmpe)(2)Cl(2)](+) and [Re(depe)(2)Cl(2)](+), respectively. The oxidation state of the final product strongly depends on the donating properties of the ligand. Each complex, however, exhibits a diffusion-controlled, reversible one-electron transfer between Re(I) and Re(II) with formal reduction potentials, E degrees ', ranging from -0.09 to -0.28 V versus a ferrocene external standard. Subsequent oxidation to Re(III) was found to be chemically irreversible. UV-vis and luminescence spectroelectrochemical techniques were used to study the spectral properties of the Re(I) and Re(II) forms. The Re(II) complexes are red in color and exhibit absorption features from 350 to 600 nm; the lowest-energy transition was assigned as a sigma(P) to dpi(Re) ligand-to-metal charge-transfer (LMCT) transition. Excitation into the lowest-energy absorption band revealed rare examples of luminescent (Phi approximately 0.07) LMCT excited states from d(5) transition-metal complexes in a room temperature solution. Structural characterization of salts of both oxidation states of [Re(dmpe)(2)(depe)](2+/+) was also performed.