
. Luminescence lifetime data Table S2 . Luminescence quantum yield data Figure S1 . 1 H, 31 P, and 19 F NMR spectra for (Ph 3 P) 2 Cu(N(p-FPh) 2 ) (3) Table S3 . Electrochemical data for compounds 1 -7 Figure S2 . Cyclic voltammagram of (Ph 3 P) 2 Cu(NTol 2 ) (2) Figure S3 . Oxidative peak current vs. ν 1/2 for (Ph 3 P) 2 Cu(NTol 2 ) (2) Figure S4 . Absorption Spectrum for (DPEphos) 2 Cu(NPh 2 ) (6) Figure S5 . Excitation/emission spectra for (Ph 3 P) 2 Cu(NPh 2 ) (1) Figure S6 . Excitation/emission spectra for (Ph 3 P) 2 Cu(NTol 2 ) (2) Figure S7 . Excitation/emission spectra for (Ph 3 P) 2 Cu(N(p-FPh) 2 ) (3) Figure S8 Excitation/emission spectra for ((p-Tol) 3 P) 2 Cu(NPh 2 ) (4) Figure S9 Excitation/emission spectra for ((p-FPh) 3 ) 2 Cu(NPh 2 ) (5) Figure S10 Excitation/emission spectra for (DPEphos) 2 Cu(NPh 2 ) (6) Figure S11 . Excitation/emission spectra for (Ph 3 P) 2 Cu(cbz) (7) Figure S12 . Luminescence decay trace and fit for (Ph 3 P) 2 Cu(NPh 2 ) (1) Figure S13 . Luminescence decay trace and fit for (Ph 3 P) 2 Cu(NTol 2 ) (2) Figure S14 . Luminescence decay trace and fit for (Ph 3 P) 2 Cu(N(p-FPh) 2 ) (3) Figure S15 . Luminescence decay trace and fit for ((p-Tol) 3 P) 2 Cu(NPh 2 ) (4) Figure S16 . Luminescence decay trace and fit for ((p-FPh) 3 ) 2 Cu(NPh 2 ) (5) Figure S17 . Luminescence decay trace and fit for (DPEphos) 2 Cu(NPh 2 ) (6) Figure S18 . Luminescence decay trace and fit for (Ph 3 P) 2 Cu(cbz) (7) Table S4. Summary of Crystallographic Data for 1-3, and 7 Figure S19 . Displacement ellipsoid representation (50%) of (Ph 3 P) 2 Cu(NPh 2 ) (1) Table S5 . Select bond lengths and angles for (Ph 3 P) 2 Cu(NPh 2 ) (1) Figure S20 . Displacement ellipsoid representation (50%) of (Ph 3 P) 2 Cu(NTol 2 ) (2) Table S6 . Select bond lengths and angles for (Ph 3 P) 2 Cu(NTol 2 ) (2) Figure S21 . Displacement ellipsoid representation (50%) of (Ph 3 P) 2 Cu(N(p-FPh) 2 ) (3) Table S7 . Select bond lengths and angles for (Ph 3 P) 2 Cu(N(p-FPh) 2 ) (3) Figure S22 . Displacement ellipsoid representation (50%) of (Ph 3 P) 2 Cu(cbz) (7) Table S8 . Select bond lengths and angles for (Ph 3 P) 2 Cu(cbz) ( 
7) References

S2

Experimental Section
General Considerations. All manipulations were carried out under a dinitrogen atmosphere using standard glovebox techniques. All solvents were deoxygenated and dried by sparging with Ar followed by passage through an activated alumina column from S.G. Water (Nashua, N.H.) Solvents were tested with a standard purple solution of benzophenone ketyl in THF to confirm effective oxygen and moisture removal. Methylcyclohexane and cyclopentane were of spectroscopic grade. Deuterated solvents were purchased from Cambridge Isotope Laboratories, Inc., were degassed, and stored over 3 Å molecular sieves prior to use. Bis-(4-fluorophenyl) 1 amine and mesityl copper(I) 2 were prepared according to literature procedures. Lithium amides were prepared from the Et 2 O or THF solutions of the corresponding aryl amines by treatment with a hexane solution of nbutyllithium at -78 °C. The stoichiometry of coordinated solvent molecules in the lithium reagents was estimated from 1 H NMR spectroscopy. Celite (Celite® 545) was dried at 300 °C under vacuum for 48 hours. Glass microfiber filters were dried prior to use by heating at 350 °C for 48 hours. All other starting reagents and materials were obtained from commercial vendors and used without further purification. Elemental analyses were performed by Midwest Microlabs (Indianapolis Indiana). NMR spectra were recorded at ambient temperature on Bruker Avance 400 MHz spectrophotometers.
H and

13
C NMR spectra are referenced to residual solvent.
31
P NMR spectra are reported relative to an external standard of 85% H 3 PO 4 (δ = 0 ppm).
19
F NMR spectra are reported relative to an external standard of C 6 F 6 (δ = -164.9 ppm) or C 6 H 5 F (δ = -113.15 ppm). UVVis absorption measurements were recorded on a Varian Cary 50 UV-Vis spectrophotometer using 1 cm path length quartz cuvettes equipped with an air-tight screw cap.
19
Electrochemistry. Electrochemical measurements were carried out in a glovebox under a dinitrogen atmosphere in a single-compartment cell using a BAS model 100/W electrochemical analyzer. A freshly polished glassy carbon electrode and a coiled platinum wire were used as the working and auxiliary electrodes, respectively. The reference electrode was Ag/AgNO 3 in THF. Samples were prepared by dissolving a small quantity (ca. 3 mg) of analyte in approximately 3 mL of a 0.3 M [(Bu) 4 N][PF 6 ] electrolyte solution in THF. The reference electrode was calibrated before and after measurements using an external ferrocene standard.
19
X-ray Crystallography Procedures. X-ray quality crystals were grown as indicated in the experimental section. Single crystals were mounted on a glass fiber using Paratone-N oil. Lowtemperature single-crystal diffraction studies were collected on a Siemens Platform three-circle diffractometer coupled to a Bruker-AXS Smart Apex CCD detector with graphite monochromated Mo Kα radiation ( λ= 0.71073 ) performing φ-and ω-scans. The structure was solved by the Patterson method using SHELXS 3 and refined against F 2 on all data by full-matrix least squares with SHELXL-97. 4 All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included at the model at geometrically calculated positions and refined using a standard riding model. The isotropic displacement parameters of the hydrogen atoms were fixed to 1.2 times the U values of the atoms they are linked to (1.5 times for methyl groups).
19
The diffraction data for (PPh 3 ) 2 Cu(NTol 2 ) (2) exhibited characteristic features of nonmerohedral twinning and was refined accordingly: 5 Two crystallographically independent domains with identical unit cell parameters were identified from the diffraction pattern using the Cell_Now 6 software included in the SHELX package. The domains were present in approximately a 60:40 ratio. The twinned data set was reduced in SAINT and absorption correction performed using TWINABS. The reflection data was written into the multi-domain HKL5 file format. At this point, the structure was refined by standard methods.
S3
A single phenyl substituent of the diphenylamide ligand in (PPh 3 ) 2 Cu(NPh 2 ) (1) was disordered over two positions with 75:25 relative occupancy. The disorder was incorporated in the final model. The unit cell also contained two half-benzene molecules located on inversion centers. The refinement of these moieties was facilitated by the use of similarity restraints on the 1,2-and 1,3-distances.
S3
Luminescence Lifetime Measurements. Analyte solutions were prepared in a nitrogen-filled glovebox by suspending a small amount (ca. 2 mg) of copper complex in ca. 20 mL of MeCy, in which they were sparingly soluble. The saturated solutions were then filtered through a glass microfiber filter into quartz fluorescence cuvettes (1 cm path length), the concentrations adjusted with additional filtered MeCy, fit with an air-tight screw cap, and brought out of the glovebox. The concentration of analyte in each sample was 1 x 10 -4 M or below. Luminescence lifetimes were determined by time-resolved phosphorescence spectroscopy as previously described. 7 The irradiation source was an Oriel nitrogen laser (Model 79111) with a 5 ns pulse width operating at approximately 3 Hz. The emitted light was dispersed in an Oriel MS-260i spectrograph with a 300 lines/mm grating and was detected by an Andor Technologies Intensified CCD camera (1024 x 128 pixels) with an onboard delay generator and a minimum gate width of 5 ns, operating in full vertical binning mode and triggered by a TTL pre-pulse from the nitrogen laser. The detector was calibrated using an Hg(Ar) pen lamp. Measurements were performed at ambient temperature. Measured values at each gate step position were accumulated from 15 pulses. All kinetic traces exhibited monoexponential decay and were fit to a first-order model. Decay constants for each sample were determined at three wavelengths at and around the emission maximum and averaged. The reported value is the average obtained from at least 2 samples. Quantum Yield Measurements. Analyte solutions were prepared in a nitrogen-filled glovebox by suspending a small amount (ca. 2 mg) of copper complex in ca. 20 mL of MeCy, in which they were sparingly soluble. The saturated solutions were then filtered through a glass microfiber filter into quartz fluorescence cuvettes (1 cm path length), the concentrations adjusted by the addition of MeCy, fit with an air-tight screw cap and brought out of the glovebox. The concentration of analyte in each sample was 1 x 10 -4 M or below. Emission spectra were collected on a SPEX Fluorolog-τ3 fluorimeter (Model FL-321, 450 W xenon lamp) using right angle detection. The optical density of each sample was kept near or below 0.1 at the wavelength of excitation and at longer wavelengths to minimize reabsorption of emitted light. Luminescence measurements were performed using a 390 nm excitation at 298 K. Excitation monochrometer slits were adjusted to allow for 3 nm resolution while the emission monochrometer slits were adjusted to allow for 5 nm resolution. Quantum yields were calculated from the measured quantities by the method of Demas and Crosby. 8 All quantum yields are reported in reference to a standard sample of perylene in benzene with a reported quantum yield value of Φ R = 0.99. 9 The reported value is the average of at least two samples. The complete emission data is provided in Table S2 . 10 Molecular orbitals and energies were determined from a singlepoint calculation using the B3LYP hybrid functional 11 and the 6-31+G* 12 basis set. Input coordinates were obtained from the solid-state structure.
S3
Synthesis of (Ph 3 P) 2 Cu(NPh 2 ) (1), Method A. A solution of triphenylphosphine (255 mg, 0.97mmol, 2 eq.) in 3 ml benzene was added to a stirring suspension of CuBr·SMe 2 (100 mg, 0.49 mmol, 1 eq.) in 3 ml benzene causing the suspended solids to dissolve. Li(NPh 2 )·1.33 Et 2 O (133 mg, 0.49 mmol, 1 eq.) was added in portions as a suspension in 3 ml benzene to the stirring copperphosphine mixture causing the immediate production of a bright green luminescence. The solution was stirred at ambient temperature for 5 h then concentrated in vacuo to a volume of 2 mL. The concentrated solution was passed through a glass microfiber filter packed with Celite. The filter was extracted with benzene until the total volume of the filtered solution was 5 mL. The solution was carefully layered with 15 mL n-pentane and allowed to stand undisturbed for 3 days after which large green-yellow crystalline blocks and needles had grown. The solution was cooled to -30 °C for 2 hr then filtered. The solids were rinsed once with n-pentane and briefly dried in vacuo. Yield: 312 mg (85%). Synthesis of (Ph 3 P) 2 Cu(NPh 2 ) (1), Method B. A solution of triphenylphosphine (72 mg, 0.27 mmol, 2 eq.) in 3 mL benzene was added to a stirring solution of mesityl copper (25 mg, 0.14 mmol, 1 eq.) in 3 mL benzene causing the yellow solution to lighten slightly. After stirring for ca. 5 minutes, diphenylamine (23 mg, 0.14 mmol, 1 eq.) in 3 mL benzene was added to the stirring copperphosphine mixture. After stirring for 3-days at room temperature, a bright green luminescent solution had developed. The solvent was concentrated in vacuo to a volume of 2 mL, filtered through a glass microfiber filter packed with Celite. 10 mL n-pentane was added and the solution cooled to -30 °C overnight, affording a bright green microcrystalline solid. The solid was filtered, rinsed with npentane, and dried briefly in vacuo. Yield: 22 mg (19%). Spectroscopic data were identical to that of the material obtained by method A.
S3
Synthesis of (Ph 3 P) 2 Cu(NTol 2 ) (2). 2 was synthesized by the same procedure as 1 method A, except Li(N(p-FPh) 2 F NMR spectra of spectroscopically pure material is provided in Figure S1 .
Synthesis of ((p-Tol) 3 P) 2 Cu(NPh 2 ) (4). 4
was synthesized by the same procedure as 1 method A, except P(p-Tol) 3 (148 mg, 0.49 mmol, 2 eq.) was used instead of triphenylphosphine. Analytically pure crystals of 4 were obtained by layering a saturated benzene solution with pentane. Yield: 136 mg (67 %). Synthesis of ((p-FPh) 3 P) 2 Cu(NPh 2 ) (5). 5 was synthesized by the same procedure as 1 method A, except P(p-FPh) 3 (196 mg, 0.53 mmol, 2 eq.) was used instead of triphenylphosphine. 5 was obtained as an analytically pure yellow solid by layering a saturated benzene solution with pentane producing crystalline material of varying morphology after 2 days. Yield: 160 mg (76 %). Synthesis of (DPEPhos)Cu(NPh 2 ) (6). 6 was synthesized by the same procedure as 1 method A, except 1 eq. DPEphos (262.0 mg, 0.49 mmol, 1 eq.) was used instead of 2 eq. triphenylphosphine. 6 was obtained as a bright yellow microcrystalline solid by layering a saturated benzene solution of the complex with pentane. Yield: 251 mg (67%). Analytically pure material was obtained by an additional recrystallization as described above. Synthesis of (Ph 3 P) 2 Cu(carbazolate) (7). 7 was synthesized by the same procedure as 1 method A, except Li(carbazolate) ·2.25 THF (81.6 mg, 0.24 mmol, 1 eq.) was used instead of Li(NPh 2 )·1.33 Et 2 O. Large, pale yellow, analytically pure crystals of 7 were obtained by layering a benzene solution with n-pentane. Yield: 121 mg (64 %). Figure S1 . Figure S18. Luminescence decay trace of (Ph 3 P) 2 Cu(cbz) (7, λ ex = 337 nm, λ em = 461 nm) with monoexponential fit. Unit cell dimensions a = 11.9487 ( Figure S20 . Displacement ellipsoid representation (50%) of (Ph 3 P) 2 Cu(NTol 2 ) (2). Hydrogen atoms and solvent (benzene) omitted for clarity. Figure S21 . Displacement ellipsoid representation (50%) of (Ph 3 P) 2 Cu(N(p-FPh) 2 ) (3). Hydrogen atoms omitted for clarity. Figure S22 . Displacement ellipsoid representation (50%) of (Ph 3 P) 2 Cu(cbz) (7). Hydrogen atoms omitted for clarity. 
S8
. Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2010

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