Identifying the first folded alkylbenzene via ultraviolet, infrared, and Raman spectroscopy of pentylbenzene through decylbenzene† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc02027a

The shortest possible single-chain alkylbenzene to exist in a folded conformation is determined using spectroscopic and theoretical techniques.

[1]  A. Goursot,et al.  Interaction between n-Alkane Chains:  Applicability of the Empirically Corrected Density Functional Theory for Van der Waals Complexes. , 2007, Journal of chemical theory and computation.

[2]  A. Fujii,et al.  Infrared spectroscopy of CH stretching vibrations of jet-cooled alkylbenzene cations by using the "messenger" technique , 2000 .

[3]  A. Fujii,et al.  Infrared Photodissociation Spectroscopy of n-Propylbenzene−Ar Cluster Cations: Charge Delocalization between the Aromatic Ring and the Alkyl Chain , 2001 .

[4]  Jonathan M. Goodman,et al.  What Is the Longest Unbranched Alkane with a Linear Global Minimum Conformation? , 1997, J. Chem. Inf. Comput. Sci..

[5]  F. Battin‐Leclerc.  Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates , 2008 .

[6]  William J. Pitz,et al.  An experimental and modeling study of surrogate mixtures of n-propyl- and n-butylbenzene in n-heptane to simulate n-decylbenzene ignition , 2014 .

[7]  Roman M. Balabin.  Enthalpy difference between conformations of normal alkanes: Raman spectroscopy study of n-pentane and n-butane. , 2009, The journal of physical chemistry. A.

[8]  T. Zwier,et al.  Mode‐selective photoisomerization in 5‐hydroxytropolone. I. Experiment , 1995 .

[9]  J. Simons,et al.  High resolution electronic spectroscopy of three n-alkylbenzenes: ethyl-, propyl-, and butylbenzene , 2002 .

[10]  N. Lüttschwager,et al.  Stretching and folding of 2-nanometer hydrocarbon rods. , 2014, Soft matter.

[11]  R. Zimmermann,et al.  Comprehensive multidimensional separation methods by hyphenation of single-photon ionization time-of-flight mass spectrometry (SPI-TOF-MS) with GC and GC×GC , 2010, Analytical and bioanalytical chemistry.

[12]  R. Zimmermann,et al.  Quasi-simultaneous acquisition of hard electron ionization and soft single-photon ionization mass spectra during GC/MS analysis by rapid switching between both ionization methods: analytical concept, setup, and application on diesel fuel. , 2011, Analytical chemistry.

[13]  J. Simons,et al.  Conformationally induced transition moment rotations in theS1←S0 electronic spectra ofn-propylbenzene andn-butylbenzene , 1997 .

[14]  William F. Murphy,et al.  Isolated C–H stretching vibrations of n‐alkanes: Assignments and relation to structure , 1984 .

[15]  B. Mishra,et al.  Influence of the substituents on the CH...π interaction: benzene-methane complex. , 2013, The journal of physical chemistry. A.

[16]  Alexander D. MacKerell,et al.  An ab initio study on the torsional surface of alkanes and its effect on molecular simulations of alkanes and a DPPC bilayer. , 2005, The journal of physical chemistry. B.

[17]  J. B. Hopkins,et al.  Vibrational relaxation in jet‐cooled alkyl benzenes. I.Absorption spectra , 1980 .

[18]  William L Jorgensen,et al.  Conformation of alkanes in the gas phase and pure liquids. , 2006, The journal of physical chemistry. B.

[19]  Daniel P. Tabor,et al.  Anharmonic modeling of the conformation-specific IR spectra of ethyl, n-propyl, and n-butylbenzene. , 2016, The Journal of chemical physics.

[20]  Matthew J. Dewitt,et al.  Hydrocarbon Group-Type Analysis of Petroleum-Derived and Synthetic Fuels Using Two-Dimensional Gas Chromatography , 2014 .

[21]  Pavel Hobza,et al.  Blue-Shifting Hydrogen Bonds. , 2000, Chemical reviews.

[22]  J. Park,et al.  Experimental and theoretical determination of the accurate CH/π interaction energies in benzene-alkane clusters: correlation between interaction energy and polarizability. , 2011, Physical chemistry chemical physics : PCCP.

[23]  J. B. Hopkins,et al.  Vibrational relaxation in jet‐cooled alkyl benzenes , 1979 .