Modulating the Electronic and Solid-State Structure of Organic Semiconductors by Site-Specific Substitution: The Case of Tetrafluoropentacenes.

The properties as well as solid-state structures, singlet fission, and organic field-effect transistor (OFET) performance of three tetrafluoropentacenes (1,4,8,11: 10, 1,4,9,10: 11, 2,3,9,10: 12) are compared herein. The novel compounds 10 and 11 were synthesized in high purity from the corresponding 6,13-etheno-bridged precursors by reaction with dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate at elevated temperatures. Although most of the molecular properties of the compounds are similar, their chemical reactivity and crystal structures differ considerably. Isomer 10 undergoes the orbital symmetry forbidden thermal [4+4] dimerization, whereas 11 and 12 are much less reactive. The isomers 11 and 12 crystallize in a herringbone motif, but 10 prefers π-π stacking. Although the energy of the first electric dipole-allowed optical transition varies only within 370 cm-1 (0.05 eV) for the neutral compounds, this amounts to roughly 1600 cm-1 (0.20 eV) for radical cations and 1300 cm-1 (0.16 eV) for dications. Transient spectroscopy of films of 11 and 12 reveals singlet-fission time constants (91±11, 73±3 fs, respectively) that are shorter than for pentacene (112±9 fs). OFET devices constructed from 11 and 12 show close to ideal thin-film transistor (TFT) characteristics with electron mobilities of 2×10-3 and 6×10-2  cm2 V-1 s-1 , respectively.

Tungsten Iodide Clusters as Singlet Oxygen Photosensitizers: Exploring the Domain of Resonant Energy Transfer at 1 eV.

The photophysics of selected tungsten iodide clusters was examined with respect to their role as a photosensitizer for the production of singlet oxygen, O2(a1Δg). We examined all-iodo octahedral clusters, [W6I8(I6)]2-, and ligand-substituted octahedral clusters, [W6I8(L6)]2-, in which the ligand, L, occupies the outer apical positions surrounding the cluster core. We also examined a square-pyramidal cluster, [W5I8(I5)]-, in which the tungsten core was presumably more accessible to diffusional encounter with ground state oxygen, O2(X3Σg-). For the compounds examined, we find pronounced cluster-dependent changes in the yield of photosensitized O2(a1Δg) production. In particular, although the iodine-encased octahedral cluster, [W6I8(I6)]2-, is an efficient O2(a1Δg) sensitizer, the pyramidal cluster, [W5I8(I5)]-, does not make O2(a1Δg) at all. The latter provides fundamental insight into the important case where the sensitizer triplet state is nearly degenerate with the O2(X3Σg-)-O2(a1Δg) transition energy at 1 eV. Our data indicate that even with near resonance, energy transfer to form O2(a1Δg) will not occur within the 3sensitizer-O2(X3Σg-) encounter pair if other more efficient channels for energy dissipation are available.

Lithium and Sodium Ion Distributions in A2- x[W6I14] Structures.

Ag2[W6I14] and A2- x[W6I14] compounds with A = Na, Li were prepared from binary tungsten iodides (W3I12) and corresponding metal iodides. Their crystal structures are analyzed on the basis of X-ray diffraction data. 7Li and 23Na solid-state NMR measurements reveal that Li+ and Na+ ions are distributed over two sites in the respective structures. These results shed some new light on A x[M6I14] with A = alkali and M = Mo, W compounds being reported with x = 1 and 2, which exhibit photophysical properties. The lithium compound is an exception in the series of A2- x[W6I14] compounds, because it is the only compound which is soluble in water.

Energy transfer in supramolecular [Crypt-RE]-[W6I14] solids.

Photophysical properties of tungsten iodides with the [W6I14]2- cluster core have been described with respect to phosphorescence and phosphorescence quenching by molecular oxygen. This process involves energy transfer from excited triplet states of the cluster onto molecular oxygen. In the present study we investigate deactivation channels of exited triplet states of the [W6I14]2- cluster towards rare earth ions. For this purpose, we synthesized several supramolecular assemblies made of [W6I14]2- clusters and metal cryptates and investigated their crystal structures and photophysical properties. UV/Vis photoexcitation of solid [Crypt-A]-[W6I14] (A = alkaline metal) and [Crypt-RE]-[W6I14] revealed phosphorescence of the cluster, respectively of the photophysically active rare earth metal (RE) center. A cluster to cryptate energy transfer is proven with a photophysically active rare earth ion by the emission of Yb3+ at 977 nm (2F5/2-2F7/2) and Nd3+ 1072 nm (4F3/2-4I11/2). These results show that an effective excitation of near-infrared-emitting rare earth ions is possible under excitation up to 550 nm with [Crypt-RE]-[W6I14] assemblies.

Photodynamic properties of tungsten iodide clusters incorporated into silicone: A2[M6I8L6]@silicone.

The light-induced antibacterial and antifungal properties of A2[M6I8L6] with M = Mo and W, A = organic cation, L = ligand have been studied. The photoactive compounds (TBA)2[W6I8(C7H7SO3)6] and (TBA)2[W6I8(COOCF3)6] have been incorporated into a permeable silicone matrix and were measured for their application in the decomposition of multi-resistant bioactive species (hospital germs) such as S. aureus and P. aeruginosa as well as fungi. In addition, we present a new high volume synthesis route for these types of cluster compounds departing from the soluble compound W6I22.