Organo- and hydrogelators based on luminescent monocationic terpyridyl platinum(II) complexes with biphenylacetylide ligands.

A series of phosphorescent terpyridyl platinum(II) complexes with ancillary biphenylacetylide ligands, namely, [(R(3)tpy)PtC≡C(biphenyl)]X (R=tBu, H, or Et(2)N; tpy=2,2';6',2''-terpyridyl; X is an anion) were synthesized and structurally characterized by various spectroscopic techniques and X-ray diffraction methods. Despite a lack of long alkyl chain(s) or hydrogen-bonding motif(s), complexes [(tpy)PtC≡C(biphenyl)]Cl and [(tBu(3)tpy)PtC≡C(biphenyl)]X (X=Cl, ClO(4), PF(6), or BF(4)) were found to gelate water and organic solvents, respectively. The self-aggregation of these complexes in solutions and the resulting gels were investigated with variable-temperature (VT) (1)H NMR spectroscopy, polarized optical microscopy, and absorption/emission spectroscopy. SEM micrographs on dry gels revealed entangled nanofibers with diameters of 20-40 nm and lengths of tens of micrometers. Powder X-ray diffraction (PXRD) study revealed various degrees of crystallinity of these fibrillar nanostructures. The substituents on both the terpyridyl and acetylide ligands and counterion of these complexes play a profound but concerted role in tuning the intermolecular metal···metal and/or π-π interactions, and hence the gelation properties.

Ligand-to-ligand charge-transfer transitions of platinum(II) complexes with arylacetylide ligands with different chain lengths: spectroscopic characterization, effect of molecular conformations, and density functional theory calculations.

The complexes [Pt(tBu(3)tpy){C[triple bond]C(C(6)H(4)C[triple bond]C)(n-1)R}](+) (n = 1: R = alkyl and aryl (Ar); n = 1-3: R = phenyl (Ph) or Ph-N(CH(3))(2)-4; n = 1 and 2, R = Ph-NH(2)-4; tBu(3)tpy = 4,4',4''-tri-tert-butyl-2,2':6',2''-terpyridine) and [Pt(Cl(3)tpy)(C[triple bond]CR)](+) (R = tert-butyl (tBu), Ph, 9,9'-dibutylfluorene, 9,9'-dibutyl-7-dimethyl-amine-fluorene; Cl(3)tpy = 4,4',4''-trichloro-2,2':6',2''-terpyridine) were prepared. The effects of substituent(s) on the terpyridine (tpy) and acetylide ligands and chain length of arylacetylide ligands on the absorption and emission spectra were examined. Resonance Raman (RR) spectra of [Pt(tBu(3)tpy)(C[triple bond]CR)](+) (R = n-butyl, Ph, and C(6)H(4)-OCH(3)-4) obtained in acetonitrile at 298 K reveal that the structural distortion of the C[triple bond]C bond in the electronic excited state obtained by 502.9 nm excitation is substantially larger than that obtained by 416 nm excitation. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations on [Pt(H(3)tpy)(C[triple bond]CR)](+) (R = n-propyl (nPr), 2-pyridyl (Py)), [Pt(H(3)tpy){C[triple bond]C(C(6)H(4)C[triple bond]C)(n-1)Ph}](+) (n = 1-3), and [Pt(H(3)tpy){C[triple bond]C(C(6)H(4)C[triple bond]C)(n-1)C(6)H(4)-N(CH(3))(2)-4}](+)/+H(+) (n = 1-3; H(3)tpy = nonsubstituted terpyridine) at two different conformations were performed, namely, with the phenyl rings of the arylacetylide ligands coplanar ("cop") with and perpendicular ("per") to the H(3)tpy ligand. Combining the experimental data and calculated results, the two lowest energy absorption peak maxima, lambda(1) and lambda(2), of [Pt(Y(3)tpy)(C[triple bond]CR)](+) (Y = tBu or Cl, R = aryl) are attributed to (1)[pi(C[triple bond]CR)-->pi*(Y(3)tpy)] in the "cop" conformation and mixed (1)[d(pi)(Pt)-->pi*(Y(3)tpy)]/(1)[pi(C[triple bond]CR)-->pi*(Y(3)tpy)] transitions in the "per" conformation. The lowest energy absorption peak lambda(1) for [Pt(tBu(3)tpy){C[triple bond]C(C(6)H(4)C[triple bond]C)(n-1)C(6)H(4)-H-4}](+) (n = 1-3) shows a redshift with increasing chain length. However, for [Pt(tBu(3)tpy){C[triple bond]C(C6H4C[triple bond]C)(n-1)C(6)H(4)-N(CH(3))(2)-4}](+) (n = 1-3), lambda(1) shows a blueshift with increasing chain length n, but shows a redshift after the addition of acid. The emissions of [Pt(Y(3)tpy)(C[triple bond]CR)](+) (Y = tBu or Cl) at 524-642 nm measured in dichloromethane at 298 K are assigned to the (3)[pi(C[triple bond]CAr)-->pi*(Y(3)tpy)] excited states and mixed (3)[d(pi)(Pt)-->pi*(Y(3)tpy)]/(3)[pi(C[triple bond]C)-->pi*(Y(3)tpy)] excited states for R = aryl and alkyl groups, respectively. [Pt(tBu(3)tpy){C[triple bond]C(C(6)H(4)C[triple bond]C)(n-1)C(6)H(4)-N(CH(3))(2)-4}](+) (n = 1 and 2) are nonemissive, and this is attributed to the small energy gap between the singlet ground state (S(0)) and the lowest triplet excited state (T(1)).

A dicationic organoplatinum(II) complex containing a bridging 2,5-bis-(4-ethynylphenyl)-[1,3,4]oxadiazole ligand behaves as a phosphorescent gelator for organic solvents.

A dicationic platinum(II) terpyridyl complex, [(tBu3tpy)Pt(OXD)Pt(tBu3tpy)](PF6)2 (tBu(3)tpy = 4,4',4"-tri-tert-butyl-2,2':6',2"-terpyridyl, OXD = 2,5-bis(4-ethynylphenyl)[1,3,4]oxadiazole) formed phosphorescent organogels in acetonitrile or in a mixture of acetonitrile and alcohol. The structure and properties of these emissive gels were analyzed by polarizing optical and confocal laser scanning microscopy, and by variable-temperature 1H NMR, UV/Vis, and emission spectroscopy. Dry gels were studied by scanning electron microscopy, powder X-ray diffraction (PXRD), and small-angle X-ray scattering (SAXS). SEM images of the dry gel revealed a network of interwoven nanofibers (diameter 12-60 nm, length >5 microm). Intermolecular pi-pi interactions between the [(tBu(3)tpy)PtC[triple bond]C] moieties could be deduced from the variable 1H NMR spectra. The PXRD and SAXS data showed that the assembly of the gelator could be represented by a rectangular 2D lattice of 68 A x 14 A. The ability of the complex to gelate a number of organic solvents is most likely due to intermolecular pi-pi interactions between the [(tBu3tpy)PtC[triple bond]C] moieties.