A Superior Synthesis of Longitudinally Twisted Acenes

Abstract

Seven longitudinally twisted acenes (an anthracene, two tetracenes,t hree pentacenes, and ah exacene) have been synthesizedb yt he addition of aryllithium reagents to the appropriate quinone precursors, followed by SnCl 2 -mediatedr eductiono ft heir diol intermediates, and severalo ft hese acenesh ave been crystallographicallyc haracterized. The new syntheses of the three previously reported twisted acenes, decaphenylanthracene (1), 9,10,11,20,21,22-hexaphenyltetrabenzo[a,c,l,n]pentacene( 2), and 9, 10,11,12,13,14,15,16-octaphenyldibenzo[a,c]tetracene (14), resulted in ar eductiono ft he number of synthetic steps.A saconsequence their overall yields werei ncreased by factors of 50-, 24-, and 66-fold, respectively.A ll of the twisted acenes yntheses reported here are suitable fort he synthesis of at least gram quantities of these remarkable hydrocarbon materials.

A Computational Physical Organic Study of a Torque, Lock, and Propagate Approach and Validation with the Synthesis of Configurationally Stable First‐Generation Helically Twisted Acenes

“…Indeed, this new torque‐lock‐propagate approach is modular and versatile and can readily be used to make a wide range of heli‐acenes of variable length with a spectrum of substituents on the acene domain. Its potential as a powerful twisted‐acene synthetic approach can be extended even further when coupled with new acene homologation methods such as those reported by the Kilway group [31, 43] …”

“…Its potential as a powerful twisted-acene synthetic approach can be extended even further when coupled with new acene homologation methods such as those reported by the Kilway group. [31,43] Experimental Section General information: All computational studies were make using either the Gaussian 09 or 16 software packages. All energy minima (S o , S 1 , and T 1 ) had zero negative frequencies.…”

Synthesis and Structure of a Longitudinally Twisted Hexacene

“…Recently, we described the rather facile synthesis of compound 3 by the addition of phenyllithium to an appropriate quinone precursor, followed by SnCl 2 ‐mediated reduction of the diol intermediate. The number of synthetic steps was reduced to three, and the overall yield was improved by 24‐fold . This result indicated that a reasonable route to hexacene 4 might be at hand.…”

“…For us, heating phencyclone ( 5 ) with naphthazarin ( 6 ) in nitrobenzene did not form the desired 11,14‐dihydroxy‐9,16‐diphenyldibenzo[ a , c ]tetracene‐10,15‐dione ( 7 ) in any appreciable amount—if at all, the majority of the product formed was a black solid that has yet to be identified. Why this is the case is not clear and made all the more curious by the fact that heating a mixture of 5 with 5,8‐dioxo‐5,8‐dihydronaphthalene‐1,4‐diyl diacetate ( 8 ) in nitrobenzene did form 7 , which was conveniently and cleanly precipitated from the reaction contents in 33 % yield by the addition of acetone (Scheme ).…”

An ICT-based fluorescence enhancement probe for detection of Sn2+ in cancer cells

“…1 Stannous chloride (SnCl 2 ) is a mild Lewis acid that is widely used as a reducing agent and catalyst in various synthetic organic operations and in the production of biodegradable polylactic acid. [2][3][4] In inorganic synthesis, SnCl 2 , which acts as an effective reducing agent, could reduce metal salts, such as silver and gold salts to their metals, Cu 2+ to Cu + , and Fe 3+ to Fe 2+ . 5 Particularly, Sn 2+ species have been used in articles of daily use, such as tinplating of steel to make tin cans, 6 added to some canned and bottled foods, 7 and mouth wash. 8 In additional, tin is an essential trace micronutrient for living organisms.…”