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Electronic structure tuning of diamondoids through functionalization
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Image of FIG. 1.
FIG. 1.

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.

Image of FIG. 2.
FIG. 2.

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.

Image of FIG. 3.
FIG. 3.

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.

Image of FIG. 4.
FIG. 4.

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.

Image of FIG. 5.
FIG. 5.

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.

Image of FIG. 6.
FIG. 6.

(Bottom to top): Adamantane-1-thiol, diamantane-4-thiol, triamantane-9-thiol, [121]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 .

Image of FIG. 7.
FIG. 7.

The HOMOs of the apically functionalized diamondoid thiols. In all cases, the HOMO is localized to the functional group.

Image of FIG. 8.
FIG. 8.

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 [121]tetramantane. The dashed line represent the IP trend for the medially functionalized diamondoid thiols.

Image of FIG. 9.
FIG. 9.

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.


Generic image for table
Table I.

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.

Generic image for table
Table II.

Ionization potentials and BPIs of the functional groups attached to either a cyclohexane ring or the 4-position of diamantane.

Generic image for table
Table III.

Adiabatic and computed IPs of the apically functionalized diamondoid thiols and respective pristine diamondoids of corresponding cage size. 30


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Electronic structure tuning of diamondoids through functionalization