Fullerenes in Aromatic Solvents: Correlation between Solvation-Shell Structure, Solvate Formation, and Solubility

Abstract

In this work, an all-atom molecular dynamics simulation technique was employed to gain insight into the dynamic structure of the solvation shell formed around C60 and phenyl-C61-butyric acid methyl ester (PCBM) in nine aromatic solvents. A new method was developed to visualize and quantify the distribution of solvent molecule orientations in the solvation shell. A strong positive correlation was found between the regularity of solvent molecule orientations in the solvation shell and the experimentally obtained solubility limits for both C60 and PCBM. This correlation was extended to predict a solubility of 36 g/L for PCBM in 1,2,4-trimethylbenze. The relationship between solvation-shell structure and solubility provided detailed insight into solvate formation of C60 and solvation in relation to solvent molecular structure and properties. The determined dependence of the solvation-shell structure on the geometric shape of the solvent might allow for enhanced control of fullerene solution-phase behavior during processing by chemically tailoring the solvent molecular structure, potentially diminishing the need for costly and environmentally harmful halogenated solvents and/or additives.

Different agglomeration properties of PC61BM and PC71BM in photovoltaic inks – a spin-echo SANS study

“…[12][13][14][15] The solubility and agglomeration 16 behaviour of different fullerenes and fullerene derivatives in organic solvents and additives, with relevance for photovoltaic applications, has been the subject of signicant research in the two last decades. 17 Studies of C 60 , [18][19][20][21][22][23][24][25][26][27][28][29][30][31] C 70 , 29,[32][33][34] PC 61 BM, 2,[23][24][25][26][35][36][37][38][39][40] 14,15,38,[41][42][43] and others 2,26,44,45 in various organic solvents, were performed using an array of techniques. These include high-performance liquid chromatography (HPLC), 2 optical absorption, [32][33][34] uorescence spectroscopy,…”

Application of the Consonance Solvent Concept for Accurate Prediction of Buckminster Solubility in 180 Net Solvents using COSMO-RS Approach

“…Unfortunately, in reports providing the values of solubility there are not sufficient information about solid phase present in the equilibrium with the saturated solutions. Although no direct clues about C60 solvates can be inferred from solubility measurements this aspect was not overlooked and attracted serious attention by many investigators [10][11][12][13][14][15][16][17][64][65][66][67][68]. For example, the dissolution properties of C60 in aromatic solvents were studied using the thermos-analytical approach [10,12] and many solid solvates were identified.…”

“…It is also worth mentioning that the reference solvent method cannot help in the cases if solid states in equilibrium with saturated solutions comprise solvates. Since, there is a vast gross of evidences [10][11][12][13][14]16,17,[64][65][66]68] that Buckminster can interact with many solvents, it is quite clear that reference solubility cannot be used neither for serious improvement of predicted solubility data nor for treating cases of unknown fusion characteristics.…”

Modeling the Solubility of C70 Fullerenes in Diverse Solvents: Role of Quantum‐mechanical Descriptors

“…Several studies,experimental as well as computational, are known in the literature to analyze the solubility of fullerenes, but mainly available for the solubility of C 60 fullerenes in diverse solvents . The in‐silico (computational) studies have an advantage over the in‐vivo and in‐vitro (experimental) studies as the former are cost effective, less laborious, and can be analyzed simultaneously for diverse solvents.…”