Charge-assisted hydrogen bonds between a tetratopic receptor and terephthalate anions assemble a switchable supramolecular framework material in water.

While numerous hydrogen-bonded organic frameworks (HOFs) have been reported, typically these cannot be prepared predictablyo ri namodular fashion. In this work, we report af amilyo fn ine diamondoid crystalline porous frameworksa ssembled via hydrogen bondingb etween polyamidinium and poly-carboxylate tectons. The frameworks are prepared at room temperature in either water or water/ alcoholm ixtures. Importantly,b oth the cationic and anionic components can be varied and additional functionality can be incorporated into the frameworks, which show good stability including to prolonged heating in DMSO or water.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Ac ombination of molecular dynamics (MD), NMR spectroscopy,a nd single crystal X-ray diffraction (SCXRD) techniquesw as used to probe the self-assemblyo fparaand meta-bis(amidinium) compoundsw ith para-, meta-, and ortho-dicarboxylates. Good concordancew as observed between the MD and experimental results. In DMSO solution, the systemsf orm several rapidly exchanging assemblies,i n part because ar ange of hydrogen bondingi nteractions is possible between the amidinium and carboxylate moieties. Upon crystallization, the majority of the systemsf orm 1D supramolecular polymers, which are held together by short NÀH···Oh ydrogen bonds.

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The synthesis of fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C≡C-1-C6H2-3,5-Et2-4-C≡CC6H4-4-C≡CH)}3] (10), which bears pendant ethynyl groups, and its reaction with [RuCl(dppe)2]PF6 to afford the heterobimetallic complex fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C≡C-1-C6H2-3,5-Et2-4-C≡CC6H4-4-C≡C-trans-[RuCl(dppe)2])}3] (11) is described. Complex 10 is available from the two-step formation of iodo-functionalized fac-tris[2-(4-iodophenyl)pyridine]iridium(III) (6), followed by ligand-centered palladium-catalyzed coupling and desilylation reactions. Structural studies of tetrakis[2-(4-iodophenyl)pyridine-N,C1′](μ-dichloro)diiridium 5, 6, fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C≡C-1-C6H2-3,5-Et2-4-C≡CH)}3] (8), and 10 confirm ligand-centered derivatization of the tris(2-phenylpyridine)iridium unit. Electrochemical studies reveal two (5) or one (6–10) Ir-centered oxidations for which the potential is sensitive to functionalization at the phenylpyridine groups but relatively insensitive to more remote derivatization. Compound 11 undergoes sequential Ru-centered and Ir-centered oxidation, with the potential of the latter significantly more positive than that of Ir(N,C′-NC5H4-2-C6H4-2)3. Ligand-centered π–π* transitions characteristic of the Ir(N,C′-NC5H4-2-C6H4-2)3 unit red-shift and gain in intensity following the iodo and alkynyl incorporation. Spectroelectrochemical studies of 6, 7, 9, and 11 reveal the appearance in each case of new low-energy LMCT bands following formal IrIII/IV oxidation preceded, in the case of 11, by the appearance of a low-energy LMCT band associated with the formal RuII/III oxidation process. Emission maxima of 6–10 reveal a red-shift upon alkynyl group introduction and arylalkynyl π-system lengthening; this process is quenched upon incorporation of the ligated ruthenium moiety on proceeding to 11. Third-order nonlinear optical studies of 11 were undertaken at the benchmark wavelengths of 800 nm (fs pulses) and 532 nm (ns pulses), the results from the former suggesting a dominant contribution from two-photon absorption, and results from the latter being consistent with primarily excited-state absorption.

Ruthenium alkynyl "star" complexes with tri(2-thienyl)-, tris(1,2,3-triazolyl)-, or triphenyl-benzene cores stabilize gold nanoparticles (AuNPs). Cyclic voltammetry, transmission electron microscopy, molecular modeling, dynamic light scattering, X-ray photoelectron spectroscopy, and energy-dispersive X-ray spectroscopy studies are consistent with ca. 5 trithienyl-or triazolylbenzene-cored star complexes decorating the exterior of each AuNP. The ca. 2.5 nm diameter (by TEM) trithienylbenzene-cored gold nanoparticle hybrids are significantly less absorbing than classical Brust nanoparticles stabilized by 1-dodecanethiol; with femtosecond pulsed radiation, they exhibit exceptionally strong saturable absorption and two-photon absorption across the visible range and into the NIR region (3,000,000 GM at 500 nm, 46,000 GM at 750 nm; 1 GM = 10 -50 cm 4 s photon -1 ).