Synthesis and optical spectroscopy of platinum-metal-containing di- and tri-acetylenic polymers

Abstract

Optical absorption and photoluminescence measurements on the title polymers, -f-Pt(PBu~), -(C-C),,,-C~C+, (m= 1, 2 ) show that there is appreciable n-electron conjugation extending through the metal sites on the chain, with a lower n-n* energy gap for the triacetylenic than for the diacetylenic compound.

Synthesis, Redox and Optical Properties of Low-Bandgap Platinum(II) Polyynes with 9-Dicyanomethylene-Substituted Fluorene Acceptors

“…Similar molecular weight distributions have been observed for other reported platinum(II) polyynes. [13,23] Compounds 1 -4 have been characterized by means of elemental analyses, mass spectrometry, IR and NMR spectroscopy to satisfaction. In each case, their IR spectra revealed the characteristic m C3C and m C3N vibrations.…”

Polyynes

“…The electronic absorption, luminescence and energy transfer properties of monodisperse branched organometallic complexes and dendrimers have been relatively unexplored, which is in contrast to that of the organometallic linear polymers described earlier [90,91,[117][118][119][120]122]. In addressing this relatively unexplored area, a series of related branched organometallic chloroplatinum(ii) and chloropalladium(ii) complexes was synthesized by the Cu(i)-catalyzed dehydrohalogenation reaction of trans-[Pt(PEt 3 ) 2 Cl 2 ] and the corresponding branched alkynes and their photophysical properties studied [128].…”

“…Since the successful synthesis of the first soluble alkynyl polymer of platinum in 1977 by Hagihara and coworkers (Scheme 10.13) [66], subsequent reports on platinum-and palladium-containing polyynyl polymers by both Hagihara and Lewis are good examples of the linearity of the trans-orientation [66,90,91].…”

“…This characteristic leads to the development of materials that may be suitable for the construction of high-efficiency energy harvesting systems and organic light emitting diodes [65]. After the successful isolation of this class of polymers in the late 1970s by Hagihara and coworkers, incorporation of Group 8, 9 and 10 metals into the one dimensional rigid-rod backbone has been achieved by Lewis [90,91], Raithby [117][118][119][120], Marder [121], Gladysz [71-74, 92, 93] and others [16].…”

Metall‐Alkinyl‐σ‐Komplexe: Synthesen und Materialien

“…Die erstmalige Isolierung eines solchen Komplexes war 1987 [88] durch Reaktion von [Pt(dppm-P,P')Cl 2 ] mit LiC CtBu in siedendem THF gelungen. Es wurde angenommen, dass die Elektronendichte und der sterische Anspruch der tert-Butylgruppe entscheidende Faktoren für die Bildung der [18,[90][91][92] Zwar ist ein zusätzlicher Schritt zur Synthese der Trimethylstannylliganden nötig (Umsetzung des Alkins mit nBuLi und danach mit Me 3 SnCl [93] ), und toxisches Me 3 ¾hnlich wie bei der Dehydrohalogenierungsmethode waren die Molekulargewichte der analogen Ni-und PdPolymere allerdings weit niedriger (M w = 20 000-30 000). Die beschriebenen Verbindungen sind alle symmetrisch, wenngleich Wrackmeyer et al [94] über eine anfängliche Bildung der unsymmetrischen Dialkinyle trans-[Pt(Et 3 P) 2 (CCR)(C CR')] (R = Me, Ph; R' = H) bei der Reaktion von trans-[Pt(Et 3 P) 2 (Cl)(CCR)] mit Me 3 SnCCR berichteten.…”