5747-23-9Relevant articles and documents
Lewis acid-catalysed formation of two-dimensional phthalocyanine covalent organic frameworks
Spitler, Eric L.,Dichtel, William R.
, p. 672 - 677 (2010)
Covalent organic frameworks (COFs) offer a new strategy for assembling organic semiconductors into robust networks with atomic precision and long-range order. General methods for COF synthesis will allow complex building blocks to be incorporated into these emerging materials. Here we report a new Lewis acid-catalysed protocol to form boronate esters directly from protected catechols and arylboronic acids. This transformation also provides crystalline boronate ester-linked COFs from protected polyfunctional catechols and bis(boronic acids). Using this method, we prepared a new COF that features a square lattice composed of phthalocyanine macrocycles joined by phenylene bis(boronic acid) linkers. The phthalocyanines stack in an eclipsed fashion within the COF to form 2.3 n pores that run parallel to the stacked chromophores. The material's broad absorbance over the solar spectrum, potential for efficient charge transport through the stacked phthalocyanines, good thermal stability and the modular nature of COF synthesis, show strong promise for applications in organic photovoltaic devices.
Formation of a hydride containing amido-zincate using pinacolborane
Ingleson, Michael J.,Nichol, Gary S.,Uzelac, Marina,Yuan, Kang
supporting information, p. 14018 - 14026 (2021/10/19)
Amido-zincates containing hydrides are underexplored yet potentially useful complexes. Attempts to access this type of zincate through combining amido-organo zincates and pinacolborane (HBPin)viaZn-C/H-BPin exchange led instead to preferential formation of amide-BPin and/or [amide-BPin(Y)]?(Y = Ph, amide, H), when the amide is hexamethyldisilazide or 2,2,6,6-tetramethylpiperidide and the hydrocarbyl group was phenyl or ethyl. In contrast, the use of a dipyridylamide (dpa) based arylzinc complex led to Zn-C/H-BPin metathesis being the major outcome. Independent synthesis and full characterisation of two LnLi[(dpa)ZnPh2] (L = THF,n= 3; L = PMDETA,n= 1) complexes,1and3, respectively, enabled reactivity studies that demonstrated that these species display zincate type reactivity (by comparison to the lower reactivity of the neutral complex (Me-dpa)ZnPh2,4, Me-dpa = 2,2′-dipyridyl-N-methylamine). This included1performing the rapid deprotonation of 4-ethynyltoluene and also phenyl transfer to α,α,α-trifluoroacetophenone in contrast to neutral complex4. Complex1reacted with one equivalent of HBPin to give predominantly PhBPin (ca.90%) and a lithium amidophenylzincate containing a hydride unit, complex7-A, as the major zinc containing product. Complex7-Atransfers hydride to an electrophile preferentially over phenyl, indicating it reacts as a hydridozincate. Attempts to react1with >1 equivalent of HBPin or with catecholborane led to more complex outcomes, which included significant borane and dpaZn substituent scrambling, two examples of which were crystallographically characterised. While this work provides proof of principle for Zn-C/H-BPin exchange as a route to form an amido-zincate containing a hydride, amido-organozincates that undergo more selective Zn-C/H-BPin exchange still are required.
Electronic Spectroscopy of 2-Phenyl-1,3,2-benzodioxaborole and Its Derivatives: Important Building Blocks of Covalent Organic Frameworks
Jimenez-Hoyos, Carlos A.,Knee, Joseph L.,Northrop, Brian H.,Ryan, Roberta P.,Savino, Cara
, p. 529 - 537 (2020/02/25)
Aryl boronate esters, such as 2-phenyl-1,3,2-benzodioxaborole (1), are important components in the formation of a variety of covalent organic frameworks. The addition of substituents on the aromatic rings of aryl boronate esters has the potential to modif
