202798-00-3Relevant articles and documents
Importance of the order of successive catalyst-transfer condensation polymerization in the synthesis of block copolymers of polythiophene and poly(p-phenylene)
Miyakoshi, Ryo,Yokoyama, Akihiro,Yokozawa, Tsutomu
, p. 1022 - 1023 (2008)
Successive catalyst-transfer condensation polymerization of a Grignard-type phenylene monomer and then a thiophene monomer with a Ni catalyst yields well-defined block copolymers of poly(p-phenylene) and polythiophene, but the reverse order of polymerization results in polymers with broad molecular weight distribution. Copyright
Chemical Potential of the Solvent: A Crucial Player for Rationalizing Host–Guest Affinities
Baudet, Karine,Guerra, Sebastiano,Piguet, Claude
, p. 16787 - 16798 (2017/10/07)
Access to reliable values of the thermodynamic constants βH,G1,1, which control simple host–guest ([HG]) association, is crucial in medicine, biology, pharmacy, and chemistry, since the optimum concentration of an effector (i.e., a drug) acting on a receptor is set to 1/βH,G1,1. Intermolecular association between charged species in polar solvents, for which water is the archetype, largely obeys this principle. Any deviation from ideality, which alters the speciation in solution, is mastered by the Debye–Hückel theory of ionic atmosphere. Much less is known for related association reactions involving neutral species in non-polar (lipophilic) media such as membranes, bilayers, or organic polymers. Taking the intermolecular association between [La(hfa)3dig] guest (hfa=hexafluoroacetylacetonate, dig=2-{2-methoxyethoxy}ethane) and tridentate polyaromatic host receptors L1–L3 in dichloromethane as a proof-of-concept, we show that the progress of the association reactions, as measured by the increase in the mole fraction of occupied sites of the receptors, disrupt the chemical potential of the solvent to such an extent that βH,G1,1 may seemingly be shifted by two orders of magnitude, thus leading to erroneous dose-response prescriptions. A simple chemical model, which considers a subset of solvent molecules in surface contact with the partners of the association reaction, restores reliable access to true and interpretable thermodynamic constants. The concomitant emergence of a concentration-dependent corrective parameter reestablishes satisfying dose-dependent response under real conditions. This “complement” to the law of mass action offers a simple method for safely taking care of the non-predictable variations of the activity coefficients of the various partners when host–guest reactions are conducted in non-polar media.
Linear bimetallic alkynylplatinum(II) terpyridyl complexes bearing p-phenylene ethynylene oligomers: Synthesis, characterization, aggregation, and photophysical properties
Xu, Peng,Wu, Haotian,Jia, Hongxing,Ye, Shifan,Du, Pingwu
, p. 2738 - 2746 (2014/06/24)
The series of luminescent bimetallic alkynylplatinum(II) terpyridyl complexes [(tBu3-tpy)PtC≡C(ArC≡C)nPt(tBu 3-tpy)](PF6)2 (I-IV; tBu3-tpy = 4,4′,4″-tritertbutyl-2,2′:6′,2″-terpyridine, Ar
