The Determination of Cis-Trans Conformations in Tetrahedral p-Phenylene Vinylene Oligomers John E. Bushnell, Paul R. Kemper, Guillermo C. Bazan, and Michael T. Bowers* Department of Chemistry & Biochemistry, UniVersity of California, Santa Barbara, California 93106 ReceiVed: May 4, 2004; In Final Form: July 15, 2004 Time-of-flight mass spectrometry and ion-mobility studies were used to probe the conformations of a tetrahedral oligo p-phenylene vinylene sample. The radical cation and sodiated parent species as well as one fragmented ion were analyzed using ion mobility. Extensive molecular mechanics modeling was used to understand the effects that secondary structure has on the observed cross sections from ion-mobility experiments. The major features in the ion-mobility spectra appear to be due to arm-arm interactions caused by cis defects near the tetrahedral core of these oligomers. 1. Introduction Conjugated organic polymers have been the object of intense research since their viability for use in optoelectronic devices was shown in the early 1990s. 1-4 They are extremely attractive for the production of devices such as organic light-emitting diodes (OLEDs) and field-effect transistors due to their ease of handling and tunability. Their properties can be tuned via chemical functionalization, and in some cases production can be accomplished via spray techniques as opposed to far more expensive methods used in processing traditional metal semi- conductors. One of the first organic polymers that has shown promise as an organic semiconductor is poly(p-phenylenevi- nylene) (PPV), usually containing alkoxy side groups to render them soluble. More recently, smaller oligomers of phenylene vinylene have been synthesized, which has enabled research on a more fundamental level due to the more precise control over their synthesis. 5-7 Properties of interest include their photophysics, morphology, and resistance to degradation. Smaller oligomers offer the advantages of better purity and synthetic control compared to larger polymers. Recently, we have used ion-mobility measurements to study the size distributions of oligo-PPVs containing five and six phenyl rings. 8 As opposed to the putative trans conformation of vinyl linkages, it was found that these PPV “arms” contained a significant amount of cis defects. As the ion-mobility apparatus was coupled to a mass spectrometer, it was clear that these defects were not due to saturated tetrahedral linkages as has been postulated for poly-PPV. 9,10 Additional results utilizing near-field single-molecule spectroscopy showed excellent agree- ment between the shape distribution of oligo-PPVs and their fluorescence anisotropy. 8 Ion mobility has also been used to determine the distribution of conformations in p-cyclophanes and various other polymers. 11-15 This technique is especially useful in sorting out different conformations for compounds of identical mass and in cases where NMR assignments are difficult or impossible. An important property for luminescent organic materials is the ability to form stable, amorphous films. 7,16 While small oligo-PPV “arms” readily form crystalline structures when deposited from solution, more exotic shapes have been sought which resist crystallization and thus exist as stable glasses. 7 One of these approaches is to join four PPV “arms” together in a tetrahedral arrangement about a central carbon atom. 16 In this paper, we use the ion-mobility technique to examine the conformations of a sample of tetrakis(4-(4′-(3′′,5′′-di-tert- butylstyryl)styryl)stilbenyl)methane, a tetrahedral oligo-PPV with each PPV “arm” containing four phenyl rings. This compound will be referred to as T4R for brevity and is shown in Figure 1. The “T” represents the tetrahedral arrangement of arms about the central sp 3 carbon atom, and the “4R” indicates that there are four phenyl rings within each arm. A fragment observed in the mass spectrum, which corresponds to the loss of one arm from T4R, will be referred to here as P4R, where the “P” indicates the planar configuration about the central carbon. With the help of molecular dynamics calculations, we identify the intramolecular interactions responsible for broad families of secondary structures seen in the ion-mobility spectra and assess the ion-mobility method as an analytical tool for measuring the distribution of defects in a sample containing a wide distribution of conformations. 2. Instrumentation The instrument used in these studies has been described previously. 17 A diagram of the instrument is shown in Figure 2. It utilizes a matrix-assisted laser desorption/ionization (MAL- DI) ion source. Ions produced in the MALDI source are accelerated using a two-stage Wiley-McLaren-type system into a 1 m long reflectron time-of-flight (TOF) mass spectrometer. For ion-mobility studies, the TOF sector is operated in linear mode (the reflectron is turned off). The mass peak of interest is gated at the end of the flight tube, decelerated, and injected * To whom correspondence may be addressed. E-mail: bowers@ chem.ucsb.edu. Figure 1. The two-dimensional representation of T4R. 7730 J. Phys. Chem. A 2004, 108, 7730-7735 10.1021/jp0480910 CCC: $27.50 © 2004 American Chemical Society Published on Web 08/31/2004