Korannülen'den polisiklik süperhalojenler tasarlamak için verimli bir strateji: Bir DFT çalışması

Öz

Süperhalojenler, elektron ilgileri (EA) ve dikey ayrılma enerjileri (VDE) halojenlerinkini aşan moleküler türler olup, ileri fonksiyonel malzemelerde umut verici uygulamalara sahiptir. Bu çalışmada, koranülenin (C₁₀H₁₀) hidrojen atomlarının güçlü elektron çekici ligandlarla (F, CN ve BO) ikame edilmesi yoluyla, aromatik iskeletin bütünlüğü korunarak, polisiklik süperhalojenler tasarlamak için bir strateji öneriyoruz. Yoğunluk fonksiyonel teorisi (DFT) ile B3LYP/6-311++G(d,p) düzeyinde yapılan hesaplamalar, kısmi ikamenin (C₁₀H₅X₅), koranülenin 0,676 eV olan EA değerini, C₁₀H₅F₅ için 1,413 eV’a, C₁₀H₅(CN)₅ için 3,016 eV’a ve C₁₀H₅(BO)₅ için 2,896 eV’a yükselttiğini göstermektedir. Bununla birlikte, bu değerler hâlâ halojen referans değerinin (3,64 eV) altında kalmaktadır. Buna karşılık, tam ikame (C₁₀X₁₀) belirgin şekilde daha yüksek elektron alıcı kapasitelere yol açmaktadır. C₁₀F₁₀ mütevazı değerlere sahipken (EA = 2,052 eV, VDE = 2,249 eV), C₁₀(CN)₁₀ ve C₁₀(BO)₁₀ sırasıyla 4,513 ve 4,458 eV EA, 4,602 ve 4,583 eV VDE değerlerine ulaşarak, kloru (3,64 eV) aşmakta ve onları gerçek polisiklik süperhalojenler olarak sağlam bir şekilde konumlandırmaktadır. Yapısal analiz, koranülen π-iskeletinin büyük ölçüde korunduğunu ve tüm türevlerde C–C bağ uzunluklarının 1,38–1,47 Å aralığında kaldığını doğrulamaktadır. Bu bulgular, C₁₀(CN)₁₀ ve C₁₀(BO)₁₀’u tamamen organik, yeni bir polisiklik süperhalojen sınıfı olarak tanıtarak, süperhalojen kimyasının kapsamını geleneksel metal- ve halojen-merkezli sistemlerin ötesine genişletmektedir.

Anahtar Kelimeler

• Süperhalojen
• Korannulen
• Dikey ayrılma enerjisi
• Polisiklik aromatik bileşikler

An efficient strategy for designing polycyclic superhalogens from corannulene: A DFT study

Öz

Superhalogens are molecular species with electron affinities (EA) and vertical detachment energies (VDE) that surpass those of halogens, offering promising applications in advanced functional materials. In this study, we propose a strategy for designing polycyclic superhalogens by substituting hydrogen atoms in corannulene (C10H10) with strongly electron-withdrawing ligands (F, CN, and BO), while maintaining the integrity of the aromatic framework. Density functional theory (DFT) calculations at the B3LYP/6-311++G(d,p) level show that partial substitution (C10H5X5) enhances the EA of corannulene (0.676 eV) to 1.413 eV for C10H5F5, 3.016 eV for C10H5(CN)5, and 2.896 eV for C10H5(BO)5. However, these values remain below the halogen benchmark (3.64 eV). In contrast, complete substitution (C10X10) yields markedly higher electron-accepting capacities. While C10F10 exhibits modest values (EA = 2.052 eV, VDE = 2.249 eV), C10(CN)10 and C10(BO)10 reach EAs of 4.513 and 4.458 eV, and VDEs of 4.602 and 4.583 eV, respectively—exceeding chlorine (3.64 eV) and firmly establishing them as true polycyclic superhalogens. Structural analysis confirms that the corannulene π-framework remains largely intact, with C–C bond lengths preserved within 1.38–1.47 Å across all derivatives. These findings introduce C10(CN)10 and C10(BO)10 as a new class of all-organic polycyclic superhalogens, broadening the scope of superhalogen chemistry beyond traditional metal- and halogen-centered systems.

Anahtar Kelimeler

• Superhalogen
• Corannulene
• Vertical detachment energy
• Polycyclic aromatic compounds

Kaynakça

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