R Aravindhan, Hu Jianping, M Ummal Momeen
Magnetic Instrumentation and Applied Optics Laboratory, Department of Physics, School of Advanced Sciences, Vellore Institute of Technology, Vellore, 632014, India.
Applied Nuclear Technology in Geosciences Key Laboratory of Sichuan Province, Chengdu University of Technology, Chengdu, People's Republic of China.
J Mol Model. 2025 Jun 14;31(7):190. doi: 10.1007/s00894-025-06407-7.
Our work demonstrates the chiral and chiroptical behavior of lower diamondoid molecules such as triamantane. Through the halogen substitution prochirality process, chirality was attained from the achiral triamantane molecule. The chiroptical behavior of chiral triamantane obtained from VCD, ROA, and ORD analysis evidences the significant chiral activity for all halogen substitutions ranging from fluorine to iodine for both S and R enantiomers. These chiral and chiroptical characteristics of the triamantane enantiomers can be tuned well through various halogen substitutions. The absolute configurations for chiral triamantane molecules are identified through the Cahn-Ingold-Prelog rule together with VCD analysis. The optical rotatory dispersion (ORD) of chiral triamantane molecules is dominant for chlorine, bromine, and iodine substitutions. Chiral triamantane molecules with various halogen substitutions also find a prominent role in pharmacology through their anisotropic charge distribution and binding abilities, tunable lipophilicity, nominal synthetic accessibility, and good bioavailability score.
The absolute configurations for chiral triamantane molecules are identified through the Cahn-Ingold-Prelog rule. To study the chiroptical behavior of chiral triamantane molecules, wB97XD and M06-2X DFT functionals are employed, and for the initial guesses, 6-311G(d,p) and MidiX basis sets are used.
我们的工作展示了诸如三环癸烷等低级类金刚石分子的手性和圆二色性。通过卤代前手性过程，从非手性的三环癸烷分子获得了手性。通过VCD（振动圆二色性）、ROA（ Raman光学活性）和ORD（旋光色散）分析得到的手性三环癸烷的圆二色性行为证明，对于从氟到碘的所有卤代，S和R对映体都具有显著的手性活性。三环癸烷对映体的这些手性和圆二色性特征可以通过各种卤代很好地调节。通过Cahn-Ingold-Prelog规则结合VCD分析确定了手性三环癸烷分子的绝对构型。手性三环癸烷分子的旋光色散（ORD）在氯、溴和碘取代中占主导地位。具有各种卤代的手性三环癸烷分子因其各向异性电荷分布和结合能力、可调的亲脂性、名义上的合成可及性和良好的生物利用度评分，在药理学中也发挥着重要作用。
通过Cahn-Ingold-Prelog规则确定手性三环癸烷分子的绝对构型。为了研究手性三环癸烷分子的圆二色性行为，采用了wB97XD和Mö6-2X DFT泛函，对于初始猜测，使用了6-311G(d,p)和MidiX基组。
