Synthesis, Structural Characterization, and Phosphorescence Properties of Trigonal Zn(II) Carbene Complexes.

The sterically demanding N-heterocyclic carbene ITr (N,N'-bis(triphenylmethyl)imidazolylidene) was employed for the preparation of novel trigonal zinc(II) complexes of the type [ZnX2(ITr)] [X = Cl (1), Br (2), and I (3)], for which the low coordination mode was confirmed in both solution and solid state. Because of the atypical coordination geometry, the reactivity of 1-3 was studied in detail using partial or exhaustive halide exchange and halide abstraction reactions to access [ZnLCl(ITr)] [L = carbazolate (4), 3,6-di-tert-butyl-carbazolate (5), phenoxazine (6), and phenothiazine (7)], [Zn(bdt)(ITr)] (bdt = benzene-1,2-dithiolate) (8), and cationic [Zn(µ2-X)(ITr)]2[B(C6F5)4]2 [X = Cl (9), Br (10), and I (11)], all of which were isolated and structurally characterized. Importantly, for all complexes 4-11, the trigonal coordination environment of the ZnII ion is maintained, demonstrating a highly stabilizing effect due to the steric demand of the ITr ligand, which protects the metal center from further ligand association. In addition, complexes 1-3 and 8-11 show long-lived luminescence from triplet excited states in the solid state at room temperature, according to our photophysical studies. Our quantum chemical density functional theory/multireference configuration interaction (DFT/MRCI) calculations reveal that the phosphorescence of 8 originates from a locally excited triplet state on the bdt ligand. They further suggest that the phenyl substituents of ITr are photochemically not innocent but can coordinate to the electron-deficient metal center of this trigonal complex in the excited state.

Structural Control of Highly Efficient Thermally Activated Delayed Fluorescence in Carbene Zinc(II) Dithiolates.

Luminescent metal complexes based on earth abundant elements are a valuable target to substitute 4d/5d transition metal complexes as triplet emitters in advanced photonic applications. Whereas CuI complexes have been thoroughly investigated in the last two decades for this purpose, no structure-property-relationships for efficient luminescence involving triplet excited states from ZnII complexes are established. Herein, we report on the design of monomeric carbene zinc(II) dithiolates (CZT) featuring a donor-acceptor-motif that leads to highly efficient thermally activated delayed fluorescence (TADF) with for ZnII compounds unprecedented radiative rate constants kTADF =1.2×106  s-1 at 297 K. Our high-level DFT/MRCI calculations revealed that the relative orientation of the ligands involved in the ligand-to-ligand charge transfer (1/3 LLCT) states is paramount to control the TADF process. Specifically, a dihedral angle of 36-40° leads to very efficient reverse intersystem-crossing (rISC) on the order of 109  s-1 due to spin-orbit coupling (SOC) mediated by the sulfur atoms in combination with a small ΔES1-T1 of ca. 56 meV.

A [2.2]Isoindolinophanyl-Based Carbene (iPC) Ligand: Synthesis, Electronic and Photophysical Properties, and Application in Photocatalysis*.

Cyclic amino(alkyl) and cyclic amino(aryl) carbenes (cAACs/cAArCs) have been established as very useful ligands for catalytic and photonic applications of transition metal complexes. Herein, we describe the synthesis of a structurally related sterically demanding, electrophilic [2.2]isoindolinophanyl-based carbene (iPC) with a [2.2]paracyclophane moiety. The latter leads to more delocalized frontier orbitals and intense green fluorescence of (HiPC)OTf (2) from an intra-ligand charge transfer (1ILCT) state in the solid state. Base-promoted synthesis of the free carbene led to an unusual ring expansion and subsequent dimerization reaction, but the beneficial ligand properties can be exploited by trapping in situ at a metal center. The iPC ligand is a very potent π-chromophore, which participates in low energy metal-to-ligand (ML)CT transitions in [RhCl(CO)2(iPC)] (4) and IL-"through-space"-CT transitions in [Au(iPC)2]OTf (5). The steric demand of the iPC leads to high stability of 5 against air, moisture, or solvent attack, and ultralong-lived green phosphorescence with a lifetime of 185 µs is observed in solution. The beneficial photophysical and electronic properties of the iPC ligand, including a large accessible π surface area, were exploited by employing highly efficient energy transfer (EnT) photocatalysis in a [2+2] styrene cycloaddition reaction using 5, which outperformed other established photocatalysts in comparison.

An Air- and Moisture-stable Zinc(II) Carbene Dithiolate Dimer Showing Fast Thermally Activated Delayed Fluorescence and Dexter Energy Transfer Catalysis.

A dimeric ZnII carbene complex featuring bridging and chelating benzene-1,2-dithiolate ligands is highly stable towards air and water. The donor-Zn-acceptor structure leads to visible light emission in the solid state, solution and polymer matrices with λmax between 577-657 nm and, for zinc(II) complexes, unusually high radiative rate constants for triplet exciton decay of up to kr =1.5×105  s-1 at room temperature. Variable temperature and DFT/MRCI studies show that a small energy gap between the 1/3 LL/LMCT states of only 79 meV is responsible for efficient thermally activated delayed fluorescence (TADF). Time-resolved luminescence and transient absorption studies confirm the occurrence of long-lived, dominantly ligand-to-ligand charge transfer excited states in solution, allowing for application in Dexter energy transfer photocatalysis.

From Terminal to Spiro-Phosphonium Acceptors, Remarkable Moieties to Develop Polyaromatic NIR Dyes.

Phosphonium-based compounds gain attention as promising photofunctional materials. As a contribution to the emerging field, we present a series of donor-acceptor ionic dyes, which were constructed by tailoring phosphonium (A) and extended π-NR2 (D) fragments to an anthracene framework. The alteration of the π-spacer of electron-donating substituents in species with terminal -+ PPh2 Me groups exhibits a long absorption wavelength up to λabs =527 nm in dichloromethane and shifted the emission to the near-infrared (NIR) region (λ=805 nm for thienyl aniline donor), although at low quantum yield (Φ<0.01). In turn, the introduction of a P-heterocyclic acceptor substantially narrowed the optical bandgap and improved the efficiency of fluorescence. In particular, the phospha-spiro moiety allowed to attain NIR emission (797 nm in dichloromethane) with fluorescence efficiency as high as Φ=0.12. The electron-accepting property of the phospha-spiro constituent outperformed that of the monocyclic and terminal phosphonium counterparts, illustrating a promising direction in the design of novel charge-transfer chromophores.

Fast and Tunable Phosphorescence from Organic Ionic Crystals.

Crystalline diphosphonium iodides [MeR2 P-spacer-R2 Me]I with phenylene (1, 2), naphthalene (3, 4), biphenyl (5) and anthracene (6) as aromatic spacers, are photoemissive under ambient conditions. The emission colors (λem values from 550 to 880 nm) and intensities (Φem reaching 0.75) are defined by the composition and substitution geometry of the central conjugated chromophore motif, and the anion-π interactions. Time-resolved and variable-temperature luminescence studies suggest phosphorescence for all the titled compounds, which demonstrate observed lifetimes of 0.46-92.23 µs at 297 K. Radiative rate constants kr as high as 2.8×105  s-1 deduced for salts 1-3 were assigned to strong spin-orbit coupling enhanced by an external heavy atom effect arising from the anion-π charge-transfer character of the triplet excited state. These rates of anomalously fast metal-free phosphorescence are comparable to those of transition metal complexes and organic luminophores that utilize triplet excitons via a thermally activated delayed fluorescence mechanism, making such ionic luminophores a new paradigm for the design of photofunctional and responsive molecular materials.

Ultra-Long Lived Luminescent Triplet Excited States in Cyclic (Alkyl)(amino)carbene Complexes of Zn(II) Halides.

The high element abundance and d10 electron configuration make ZnII -based compounds attractive candidates for the development of novel photoactive molecules. Although a large library of purely fluorescent compounds exists, emission involving triplet excited states is a rare phenomenon for zinc complexes. We have investigated the photophysical and -chemical properties of a series of dimeric and monomeric ZnII halide complexes bearing a cyclic (alkyl)(amino)carbene (cAAC) as chromophore unit. Specifically, [(cAAC)XZn(µ-X)2 ZnX(cAAC)] (X=Cl (1), Br (2), I (3)) and [ZnX2 (cAAC)(NCMe)] (X=Br (4), I (5)) were isolated and fully characterized, showing intense visible light photoluminescence under UV irradiation at 297 K and fast photo-induced transformation. At 77 K, the compounds exhibit improved stability allowing to record ultra-long lifetimes in the millisecond regime. DFT/MRCI calculations confirm that the emission stems from 3 XCT/LEcAAC states and indicate the phototransformation to be related to asymmetric distortion of the complexes by cAAC ligand rotation. This study enhances our understanding of the excited state properties for future development and application of new classes of ZnII phosphorescent complexes.

Synthesis and Fluorescence Studies of Diborene Coinage Metal Complexes.

Nine different coinage metal (Cu, Ag) π complexes of diborenes with various anionic diborene (aryl, heteroaryl) and metal substituents (Cl, Br, C6F5, C2SiMe3), stabilizing neutral donors (N-heterocyclic carbene = NHC, phosphine), configurations (cis/trans, acyclic/cyclic diborene), and charges (neutral, cationic) were synthesized and characterized by multinuclear NMR spectroscopy and X-ray crystallographic analyses. Their optical properties were investigated by UV-vis absorption and steady-state as well as time-resolved luminescence spectroscopy in solution and the solid state to gain insights into the excited-state behavior of this unusual class of photoactive compounds and to provide structure-property relationships. The structural and electronic modification of the (B═B)···M motif greatly influences not only the visible light absorption but also the photostability and quantum yields, which can reach high values of up to f = 0.42. The lifetimes are found in the nanosecond regime, providing estimated radiative rate constants over a wide range of kr = 1.3-14 × 107 s-1, indicative of fluorescence. Intersystem crossing (ISC) is sufficiently slow for prompt emission from the S1 state to be observed, while the spin-orbit coupling in the T1 state is too weak for phosphorescence to occur at room temperature. ISC can be accelerated, however, by modifying diborene ligand substitution and the coinage metal center, hinting at the potential for exploiting the properties of long-lived triplet excited states of metal diborene complexes in the future.

Multiple Emission of Phosphonium Fluorophores Harnessed by the Pathways of Photoinduced Counterion Migration.

In the emerging field of intramolecular charge transfer induced counterion migration, we report the new insights into photophysical features of luminescent donor-acceptor phosphonium dyes (D-π-)n A+ [X- ] (π=-(C6 H4 )x -). The unique connectivity of the phosphorus atom affords multipolar molecules with a variable number of arms and the electronic properties of the acceptor group. In the ion-paired form, the transition from dipolar to quadrupolar configuration enhances the low energy migration-induced band by providing the additional pathways for anion motion. The multipolar architecture, adjustable lengths of the π-spacers and the nature of counterions allow for efficient tuning of the emission and achieving nearly pure white light with quantum yields around 30 %. The methyl substituent at the phosphorus atom reduces the rate of ion migration and suppresses the red shifted bands, simultaneously improving total emission intensity. The results unveil the harnessing of the multiple emission of phosphonium fluorophores by anion migration via structure and branching of donor-acceptor arms.

Ditopic Phosphide Oxide Group: A Rigidifying Lewis Base to Switch Luminescence and Reactivity of a Disilver Complex.

Heterodentate phosphines containing anionic organophosphorus groups remain virtually unexplored ligands in the coordination chemistry of coinage metals. A hybrid phosphine-phosphine oxide (o-Ph2PC6H4)2P(O)H (HP3O) readily forms the disilver complex [Ag2(P3O)2] (1) upon deprotonation of the (O)P-H fragment. Due to the electron-rich nature, the anionic phosphide oxide unit in 1 takes part in efficient intermolecular hydrogen bonding, which has an unusual and remarkably strong impact on the photoluminescence of 1, changing the emission from red (644 nm) to green-yellow (539 nm) in the solid. The basicity of the R2(O)P- group and its affinity for both inter- and intramolecular donor-acceptor interactions allow converting 1 into hydrohalogenated (2, 3) and boronated (4) derivatives, which reveal a gradual hypsochromic shift of luminescence, reaching the wavelength of 489 nm. Systematic variable-temperature analysis of the excited state properties suggests that thermally activated delayed fluorescence is involved in the emission process. The long-lived excited states for 1-4, the energy of which is largely regulated by means of the phosphide oxide unit, are potentially suitable for triplet energy transfer photocatalysis. With the highest T1 energy among 1-4, complex 4 demonstrates excellent photocatalytic activity in a [2+2] cycloaddition reaction, which has been realized for the first time for silver(I) compounds.

Cationic Organophosphorus Chromophores: A Diamond in the Rough among Ionic Dyes.

Tunable electron-accepting properties of the cationic phosphorus center, its geometry and unique preparative chemistry that allows combining this unit with diversity of π-conjugated motifs, define the appealing photophysical and electrochemical characteristics of organophosphorus ionic chromophores. This Minireview summarizes the achievements in the synthesis of the π-extended molecules functionalized with P-cationic fragments, modulation of their properties by means of structural modification, and emphasizes the important effect of cation-anion interactions, which can drastically change physical behavior of these two-component systems.

Linear Carbene Pyridine Copper Complexes with Sterically Demanding N,N'-Bis(trityl)imidazolylidene: Syntheses, Molecular Structures, and Photophysical Properties.

The sterically demanding carbene ITr (N,N'-bis(triphenylmethyl)imidazolylidene) was used as a ligand for the preparation of luminescent copper(I) complexes of the type [(ITr)Cu(R-pyridine/R'-quinoline)]BF4 (R = H, 4-CN, 4-CHO, 2,6-NH2, and R' = 8-Cl, 6-Me). The selective formation of linear, bis(coordinated) complexes was observed for a series of pyridine and quinoline derivatives. Only in the case of 4-cyanopyridine a one-dimensional coordination polymer was formed, in which the cyano group of the cyanopyridine ligand additionally binds to another Cu atom in a bridging manner, thus leading to a trigonal planar coordination environment. In contrast, employing sterically less demanding monotrityl-substituted carbene 3, no (NHC)Cu-pyridine complexes could be prepared. Instead, a bis-carbene complex [(3)2Cu]PF6 was obtained which showed no luminescence. All linear pyridine/quinoline coordinated complexes show weak emission in solution but intense blue to orange luminescence doped with 10% in PMMA films and in the solid state either from triplet excited states with unusually long lifetimes of up to 4.8 ms or via TADF with high radiative rate constants of up to 1.7 × 105 s-1 at room temperature. Combined density functional theory and multireference configuration interaction calculations have been performed to rationalize the involved photophysics of these complexes. They reveal a high density of low-lying electronic states with mixed MLCT, LLCT, and LC character where the electronic structures of the absorbing and emitting state are not necessarily identical.

The distinct O2 quenching mechanism between fluorescence and phosphorescence for dyes adsorbed on silica gel.

We herein aim to probe the emission quenched by O2 on silica gel. Our special focus is on the O2 quenching of the fluorescence of a series of organic D-π-A phosphonium compounds 1-3. The results show that the O2 quenching rate constants for the fluorescence of 1-3 are on the order of 1010 M-1 s-1, which are nearly on the same order as those measured for 1-3 and common organic compounds in solution. In yet another approach, the study of O2 quenching of phosphorescence in the solid phase indicates that the O2 quenching rate constant for the triplet state, i.e., , is smaller than by two orders of magnitude. Detailed investigation indicates that this distinction stems from the intrinsic O2 quenching rate constants for the singlet and triplet states subsequent to the formation of collisional complexes. In the absence of the solvent cage effect, is greatly influenced by the formation energy of the O2-dye CT complex, whereas in the solid phase is a nearly diffusion-controlled rate. Due to the larger distinction between and in the solid phase, O2 quenching of fluorescence is efficient for dyes in the solid phase. This leads to a feasible application of sensing O2 with regular fluorescent dyes adsorbed on porous solid substrates.

Diffraction on periodic surface microrelief grating with positive or negative optical anisotropy.

Diffraction optical elements (DOE) are important elements of systems for images displaying and processing. The DOE materials with both positive and negative birefringence enhance performances and functionality of such systems. We have calculated the diffraction of rays passing through optically anisotropic grating with surface microrelief by using our original Exedeep software. At the first time the diffraction parameters for both transmitted and reflected TE- and TM-waves are calculated for materials with both positive and negative optical anisotropy. The simulation results are to be used to create DOE for the visible, UV, IR and THz ranges.

Intramolecular Phosphacyclization: Polyaromatic Phosphonium P-Heterocycles with Wide-Tuning Optical Properties.

Rationally designed cationic phospha-polyaromatic fluorophores were prepared through intramolecular cyclization of the tertiary ortho-(acene)phenylene-phosphines mediated by CuII triflate. As a result of phosphorus quaternization, heterocyclic phosphonium salts 1 c-3 c, derived from naphthalene, phenanthrene, and anthracene cores, exhibited very intense blue to green fluorescence (Φem =0.38-0.99) and high photostability in aqueous medium. The structure-emission relationship was further investigated by tailoring the electron-donating functions to the anthracene moiety to give dyes 4 c-6 c with charge-transfer character. The latter significantly decreases the emission energy to reach near-IR region. Thus, the intramolecular phosphacyclization renders an ultra-wide tuning of fluorescence from 420 nm (1 c) to 780 nm (6 c) in solution, extended to 825 nm for 6 c in the solid state with quantum efficiency of approximately 0.07. The physical behavior of these new dyes was studied spectroscopically, crystallographically, and electrochemically, whereas computational analysis was used to correlate the experimental data with molecular electronic structures. The excellent stability, water solubility, and attractive photophysical characteristics make these phosphonium heterocycles powerful tools in cell imaging.

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 Facile Molecular Machine: Optically Triggered Counterion Migration by Charge Transfer of Linear Donor-π-Acceptor Phosphonium Fluorophores.

The D-π-A type phosphonium salts in which electron acceptor (A=-+ PR3 ) and donor (D=-NPh2 ) groups are linked by polarizable π-conjugated spacers show intense fluorescence that is classically ascribed to excited-state intramolecular charge transfer (ICT). Unexpectedly, salts with π=-(C6 H4 )n - and -(C10 H6 C6 H4 )- exhibit an unusual dual emission (F1 and F2 bands) in weakly polar or nonpolar solvents. Time-resolved fluorescence studies show a successive temporal evolution from the F1 to F2 emission, which can be rationalized by an ICT-driven counterion migration. Upon optically induced ICT, the counterions move from -+ PR3 to -NPh2 and back in the ground state, thus achieving an ion-transfer cycle. Increasing the solvent polarity makes the solvent stabilization dominant, and virtually stops the ion migration. Providing that either D or A has ionic character (by static ion-pair stabilization), the ICT-induced counterion migration should not be uncommon in weakly polar to nonpolar media, thereby providing a facile avenue for mimicking a photoinduced molecular machine-like motion.

Luminescence Thermochromism of Gold(I) Phosphane-Iodide Complexes: A Rule or an Exception?

A series of gold(I) iodide complexes 1-11 have been prepared from di-, tri-, and tetraphosphane ligands. Crystallographic studies reveal that the di- (1-7) and tetrametallic (11) compounds feature linearly coordinated gold(I) ions with short aurophilic contacts. Their luminescence behavior is determined by the combined influence of the phosphane properties, metal-metal interaction, and intermolecular lattice-defined interactions. The proposed variable contribution of 3 (X+M)-centered (X=halogen; M=metal) and 3 XLCT (halogen to ligand charge transfer) electronic transitions into the lowest lying excited state, which is influenced by supramolecular packing, is presumably responsible for the alteration of room-temperature emission color from green (λ=545 nm, for 11) to near-IR (λ=698 nm, for 2). Dinuclear compounds 6 and 7 exhibit distinct luminescence thermochromism with a blueshift up to 5750 cm-1 upon cooling. Such dramatic change of emission energy is assigned to the presence of two coupled triplet excited states of 3 ππ* and 3 (X+M)C/3 XLCT nature, the presence of which depends on both molecular structure and the crystal lattice arrangement.

Cyanide-Assembled d10 Coordination Polymers and Cycles: Excited State Metallophilic Modulation of Solid-State Luminescence.

The series of cyanide-bridged coordination polymers [(P2 )CuCN]n (1), [(P2 )Cu{M(CN)2 }]n (M=Cu 3, Ag 4, Au 5) and molecular tetrametallic clusters [{(P4 )MM'(CN)}2 ]2+ (MM'=Cu2 6, Ag2 7, AgCu 8, AuCu 9, AuAg 10) were obtained using the bidentate P2 and tetradentate P4 phosphane ligands (P2 =1,2-bis(diphenylphosphino)benzene; P4 =tris(2-diphenylphosphinophenyl)phosphane). All title complexes were crystallographically characterized to reveal a zig-zag chain arrangement for 1 and 3-5, whereas 6-10 possess metallocyclic frameworks with different degree of metal-metal bonding. The d10 -d10 interactions were evaluated by the quantum theory of atoms in molecules (QTAIM) computational approach. The photophysical properties of 1-10 were investigated in the solid state and supported by theoretical analysis. The emission of compounds 1 and 3-5, dominated by metal-to-ligand charge transfer (MLCT) transitions located within {CuP2 } motifs, is compatible with thermally activated delayed fluorescence (TADF) behaviour and a small energy gap between the T1 and S1 excited states. The luminescence characteristics of 6-10 are strongly dependent on the composition of the metal core; the emission band maxima vary in the range 484-650 nm with quantum efficiency reaching 0.56 (6). The origin of the emission for 6-8 and 10 at room temperature is assigned to delayed fluorescence. AuCu cluster 9, however, exhibits only phosphorescence that corresponds to theoretically predicted large value ΔE(S1 -T1 ). DFT simulation highlights a crucial impact of metallophilic bonding on the nature and energy of the observed emission, the effect being greatly enhanced in the excited state.

Nonadiabatic nuclear dynamics of the ammonia cation studied by surface hopping classical trajectory calculations.

The Landau-Zener (LZ) type classical-trajectory surface-hopping algorithm is applied to the nonadiabatic nuclear dynamics of the ammonia cation after photoionization of the ground-state neutral molecule to the excited states of the cation. The algorithm employs a recently proposed formula for nonadiabatic LZ transition probabilities derived from the adiabatic potential energy surfaces. The evolution of the populations of the ground state and the two lowest excited adiabatic states is calculated up to 200 fs. The results agree well with quantum simulations available for the first 100 fs based on the same potential energy surfaces. Three different time scales are detected for the nuclear dynamics: Ultrafast Jahn-Teller dynamics between the excited states on a 5 fs time scale; fast transitions between the excited state and the ground state within a time scale of 20 fs; and relatively slow partial conversion of a first-excited-state population to the ground state within a time scale of 100 fs. Beyond 100 fs, the adiabatic electronic populations are nearly constant due to a dynamic equilibrium between the three states. The ultrafast nonradiative decay of the excited-state populations provides a qualitative explanation of the experimental evidence that the ammonia cation is nonfluorescent.