A graphical overview of the three parameters studied in this work. The left branch is the type of functionalization, the center branch the size of the host cluster, and the right branch is the functionalization site.
The valence spectra of diamantane functionalized at the apical position with –OH (top), –SH (middle), and –NH2 (bottom) groups. The ionization potentials, denoted by black arrows in the figure, change drastically depending on which functional group is attached to the diamantane cage. The dashed line is an optical guide as to where the cage-structure edge might be found.
The HOMOs of the three differently functionalized diamantanes (bottom row, increasing electronegativity [BPI] from left to right) as compared to the HOMO of pristine diamantane.
The valence spectra of cyclohexane and cyclohexane functionalized with –OH (top), –SH (middle), and –NH2 (bottom) groups. The ionization potentials are denoted by black arrows. The dashed line gives an idea of where the electronic states localized on the ring structure can be found.
The shifts of IPs (bottom) and cage state IPs (top) between the pristine and the functionalized cyclohexane and diamantane compounds. The electronegativities (BPIs) are marked with crosses, the shifts of cyclohexane compounds with squares, and the shifts of diamantane compounds with rhombi.
(Bottom to top): Adamantane-1-thiol, diamantane-4-thiol, triamantane-9-thiol, tetramantane-6-thiol, and [1(2, 3)4]pentamantane-7-thiol. The dashed gray line illustrates the IP trend and the black arrows denote individual IPs, listed in Table III .
The HOMOs of the apically functionalized diamondoid thiols. In all cases, the HOMO is localized to the functional group.
Diamondoids functionalized on the medial position (solid lines) overlaid on diamondoids functionalized on the apical position (shaded areas, also shown in Fig. 6 ). From bottom to top, the spectra shown are from the host clusters diamantane, triamantane, and tetramantane. The dashed line represent the IP trend for the medially functionalized diamondoid thiols.
Comparison of the vibrational structure of the HOMO thiol states in apically (bottom) and side (top) functionalized diamantane. Blue rings represent experimental data, the solid black lines are the sum of the fit components, the thin red line the fit residual, and the solid gray lines are the first four individual fit components.
Experimental parameters used during the experiments. The resolution varies between the samples as a consequence of the limited sample amount for the functionalized higher diamondoids.
Ionization potentials and BPIs of the functional groups attached to either a cyclohexane ring or the 4-position of diamantane.
Adiabatic and computed IPs of the apically functionalized diamondoid thiols and respective pristine diamondoids of corresponding cage size. 30
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