The Unusual Self-Organization of Dialkyldithiophosphinic Acid Self-Assembled Monolayers on Ultrasmooth Gold

作者：Miller Michael S; San Juan Ronan R; Ferrato Michael Anthony; Carmichael Tricia Breen^*

来源：Journal of the American Chemical Society, 2014, 136(11): 4212-4222.

DOI：10.1021/ja411140j

We report the formation and characterization of self-assembled monolayers (SAMs) of dialkyldithiophosphinic acid adsorbates [CH3(CH2)(n)](2)P(S)-SH (R(2)DTPA) (n = 5, 9, 11, 13, 15) on ultrasmooth gold substrates prepared by the template stripping method. The SAMs were characterized using X-ray photoelectron spectroscopy, reflection absorption infrared spectroscopy, contact angle measurements, lateral force microscopy, and electrochemical impedance spectroscopy. The data show these SAMs exhibit an unusual trend in alkyl chain crystallinity; SAMs formed from adsorbates with short alkyl chains (n = 5) are ordered and crystalline, and the alkyl groups become increasingly disordered and liquidlike as the number of methylene units is increased. This trend is the opposite of the typical behavior exhibited by n-alkanethiolate SAMs, in which the alkyl layer becomes more crystalline and ordered as the alkyl chain length is increased. We discuss four factors that operate together to determine how R(2)DTPA self-organize within SAMs on TS gold: (i) adsorbate substrate interactions; (ii) gold substrate morphology; (iii) lateral van der Waals interactions between alkyl groups; and (iv) steric demands of the alkyl groups. We also present a model for the structures of these SAMs on the basis of consideration of the data and the structural parameters of a model (n)Bu(2)DTPA adsorbate. In this model, interdigitation of short alkyl chains stabilizes a trans-extended, crystalline arrangement and produces an ordered alkyl layer. As the alkyl chain length is increased, the increased steric demands of the alkyl groups lead to liquidlike, disorganized alkyl layers.

• 出版日期2014-3-19