Parthasarathy Venkatakrishnan

De novo design for functional amorphous materials: synthesis and thermal and light-emitting properties of twisted anthracene-functionalized bimesitylenes.

The unique structural attributes inherent to D(2d)-symmetric rigid tetraarylbimesityls render their close packing in the solid state difficult. We have exploited the indisposed tendency of such modules based on the bimesityl scaffold toward crystallization to design a novel class of amorphous functional materials with high glass transition temperatures and thermal stability (T(d) > 400 degrees C). It is shown that a variety of 2- and 4-fold anthracene-functionalized bimesityls, 1-7, that exhibit excellent amorphous properties (T(g) = ca. 190-330 degrees C) can be readily prepared via facile Pd(0)-mediated cross-coupling strategies. As the communication between the bimesityl core and the anchored anthracenes is negligible or only marginal, the trends observed for luminescence of model constituent anthracenes are reproduced in the condensed-phase photoluminescence and electroluminescence of 1-7. In other words, the emission characteristics, i.e., lambda(max) and quantum yields, are readily modulated via appropriate modification of the fluorophores. The functional behavior of this unique class of amorphous materials based on the bimesityl scaffold is demonstrated by fabrication of OLED devices. The 2-fold functionalized derivatives 1 and 2 lend themselves to sublimation techniques, so that the electroluminescence is captured with high efficiencies at low turn-on voltages (3.5-6.5 V). The device ITO/NPB (400 A)/1% 2:MADN (400 A)/TPBI (400 A)/LiF (10 A)/Al (1500 A) for 2 yields the highest luminance of approximately 13,900 cd/m(2) at 17.5 V, a maximum luminance efficiency of approximately 7.4 cd/A at 4.5 V, and a power efficiency of approximately 5.3 lm/W at 4.0 V. Further, at a brightness of 800 cd/m(2) and a current density of 13.8 mA/cm(2), the device is found to exhibit excellent luminance efficiency of 5.8 cd/A, external quantum efficiency of 4.3% with a power efficiency of 2.2 lm/W, and pure blue light with a CIE(x,y) (x = 0.13, y = 0.18). The performance characteristics of the devices fabricated for 1 and 2 are remarkable. Although the 4-fold functionalized systems did not permit sublimation leading to spin-coating as a means for device fabrication, the observed electroluminescence for 4 and 5 attests to a broader scope and applicability of this new category of amorphous molecules for application in OLEDs.

Nondoped Pure-Blue OLEDs Based on Amorphous Phenylenevinylene-Functionalized Twisted Bimesitylenes

The twisted bimesitylene scaffold hinders crystallization and imparts amorphous nature to the oligophenylenevinylenes (OPVs) generated by 2- and/or 4-fold functionalization. The resultant phenylenevinylenes 1-5 with unique molecular topology exhibit excellent thermal and solid-state luminescence properties. The amorphous nature permits their application as pure-blue emissive materials in OLEDs. Under nondoped conditions, the device performances observed surpass those for analogous and simple oligophenylenevinylenes known so far; for example, the device based on OPV 2 as an emitting material and structurally analogous Bim-DPAB as a hole-transporting material yields pure-blue electroluminescence with an external quantum efficiency of ca. 4.70% at 20 mA/cm(2), which is higher than those reported for nondoped pure-blue OPV emitters.

Novel photochromism of differently-linked bis-benzopyrans†

The unique photochromic bis-chromene 5 incorporates the structural attributes of both 3 and 4 . UV-vis irradiation of 5 leads to a dark brown colour, which is formed by mixing the purple and red colours observed for the photolysates of 3 and 4 , respectively.

Molecular self-assembly: 4-formylcoumarins as versatile skeletons for complementary multipoint association via weak (C–H⋯O, C–H⋯F and C–X⋯OC) interactions

The substituted 4-formylcoumarins feature remarkable skeletons for molecular edge-to-edge self-assembly via complementary multipoint weak C–H⋯O, C–H⋯F and C–X⋯OC interactions, as revealed by the X-ray crystal structure analyses of 1–6. It is shown that the formylcoumarins 1–6 can exploit as many as 6–10 weak interactions despite being structurally so simple. The edge-to-edge association via6 complementary hydrogen bonds in 1, 2, and 4 leads to 1-dimensional molecular arrays (tapes/strands), which get interconnected by C–H⋯O/C–X⋯OC noncovalent hydrogen/halogen bonds to form 2-dimensional sheets. The substitution of a hydrogen by fluoro group as in 5 and 6 leads to a dramatic change in the crystal packing, thereby implying the preponderant influence of C–H⋯F interactions over C–H⋯O interactions in at least the cases studied herein.

Metal-Free Oxidative C–C Coupling of Arylamines Using a Quinone-Based Organic Oxidant

A variety of arylamines are shown to undergo oxidative C-C bond formation using quinone-based chloranil/H+ reagent as the recyclable organic (metal-free) oxidant system to afford benzidines/naphthidines. Arylamines (3°/2°) designed with various substituents were employed to understand the steric as well as electronic preferences of oxidative dimerization, and a mechanism involving amine radical cation has been proposed. The tetraphenylbenzidine derivative obtained via oxidative C-C coupling has been further converted to blue-emissive hole-transporting material via a simple chemical transformation. This study highlights the preparation of novel HTMs in a simple, economic, and efficient manner.