Supramolecular Ruthenium–Alkynyl Multicomponent Architectures: Engineering, Photophysical Properties, and Responsiveness to Nitroaromatics

Abstract

A series of H-bonded supramolecular architectures were built from monofunctional M−CC−R and bifunctional R−CC−M−CC−R trans-alkynylbis(1,2-bis(diphenylphosphino)ethane)ruthenium(II) complexes and π-conjugated modules containing 2,5-dialkoxy-p-phenylene. Incorporation on each partner of a cyanuric end and of the complementary Hamilton receptor provided the necessary means to keep the constituents together via strong hydrogen bonding. Characterization of all architectures has been performed on the basis of NMR and photophysical methods. In particular, the formation of a Hamilton receptor/cyanuric acid complex has been exemplified by an X-ray single-crystal structure determination. Both self-assembly and accurate modification of the complementary blocks were ensured in such a way that the resulting materials maintain the responsiveness of the electron-rich 2,5-dialkoxy-p-phenylene spacers toward nitroaromatics.

Linear and Third-Order Nonlinear Optical Properties of Fe(η5-C5Me5)(κ2-dppe)- and trans-Ru(κ2-dppe)2-Alkynyl Complexes Containing 2-Fluorenyl End Groups

“…In line with previous reports, ,, we could not detect any luminescence originating from the first MLCT state of most of the new M­(II) complexes investigated. Thus, along with 1a , b , , only in the case of Ru­(II) complex 2b could a very weak emission from the MLCT state be determined, as expected for a class of compounds known to be luminescence quenchers . In several instances, selected bis-alkynyl complexes have been shown to be emissive from their first excited state.…”

“…Thus, along with 1a-b, [24][25] only in the case of the Ru(II) complex 2b could a very weak emission from the MLCT state be determined, as expected for a class of compounds known to be luminescence quenchers. 66 In several instances, selected bis-alkynyl complexes have been shown to be emissive from their first excited state. However, in these cases, either the MLCT character of the emissive state is totally absent, as in 19a-b, 8 or it is strongly admixed with another character (such as LLCT, for instance).…”

Syntheses and molecular structures of trans-bis(alkynyl) tetrakis-triethylphosphite ruthenium complexes

“…The chemistry of trans-bis(alkynyl) complexes of ruthenium has been extensively developed over the past decades, and whilst the vast majority are supported by ancillary phosphine ligands, [1][2][3][4] examples with other supporting ligand sets, including, for example, mixed phosphine-carbonyl [5,6] or N-heterocyclic carbenecarbonyl [7] ligand sets, macrocyclic amines and dioxodiazamacrocyles [8,9] are also known. In addition to finding extensive application as building blocks and donors for the construction of NLO active materials, [10,11] including chemically and redoxswitchable examples, [12,13] donor molecules within solar cells [14][15][16] and applications as sensors, [17] trans-[Ru(C≡CR) 2 (dppe) 2 ] [dppe = 1,2bis(diphenylphosphino)ethane] complexes systems commonly feature in designs of metal-containing molecular wires. [18,19] The development of mechanically controlled break-junctions and molecular junctions based on the use of a scanning tunnelling microscope (STM) tip to contact a single molecule now allows the investigation of molecular compounds and complexes at the molecular level as active components in prototypical electronic devices.…”

Supramolecular Architectures Incorporating Hydrogen‐Bonding Barbiturate Receptors

“…Indeed, a multisensor array with two or four chiral receptors was able to discriminate between seven chiral phosphate anions (AMP, ADP, ATP, CMP, GMP, inorganic phosphate, and inorganic pyrophosphate) with 100 % classification accuracy 8. A supramolecular ruthenium–alkynyl multicomponent assembly, which shows responsiveness to nitroaromatics was also recently described 9…”