Reply to “Comment on ‘How the Number and Location of Lithium Atoms Affect the First Hyperpolarizability of Graphene’”

Reply to “Comment on ‘How the Number and Location of Lithium Atoms Affect the First Hyperpolarizability of Graphene’

Quantum Chemical Research on Structures, Linear and Nonlinear Optical Properties of the Li@<i>n</i>-Acenes Salt (<i>n</i> = 1, 2, 3, and 4)

On the basis of the n-acenes (n = 1, 2, 3 and 4), the α-Li@n-acenes and β-Li@n-acenes salts were selected to investigate how increasing the number n of conjugated benzenoid rings affects the linear and nonlinear optical responses. The α-Li@n-acenes and β-Li@n-acenes salts are obtained by a lithium atom substituting the α-H and β-H, respectively. In the present work, both ab initio (HF and MP2) and DFT (B3LYP, BhandHLYP, M05-2X, and CAM-B3LYP) methods are adopted to calculate the polarizability (α0) and first hyperpolarizability (βtot) of the α-Li@n-acenes and β-Li@n-acenes salts. MP2 results show that the α0 values of both classes of lithium salts increase with increasing number n of conjugated benzenoid rings. Interestingly, we found that the βtot values of α-Li@n-acenes and β-Li@n-acenes salts take on opposite trends: the βtot values of α-Li@n-acenes are decreasing slowly (2187 for α-Li@benzene > 1978 for α-Li@naphthalene > 1898 for α-Li@anthrecene > 1830 au for α-Li@tetracene) and inceasing remarkably (2738 for β-Li@naphthalene n-acenes. Furthermore, we found that the βtot values (2738−3314 au) of the β-Li@n-acenes are larger than those of the α-Li@n-acenes (1830−2187 au). On the other hand, comparing the results of different methods, the βtot values obtained by the M05-2X and CAM-B3LYP methods reproduce the polarizability and first hyperpolarizability of the α-Li@n-acenes and β-Li@n-acenes salts well, which test and verify the results of the MP2 method. Our present work may be beneficial to development of high-performance organic NLO optical materials

How the Number and Location of Lithium Atoms Affect the First Hyperpolarizability of Graphene

How do the number and location of lithium atoms affect the first hyperpolarizability (βtot) of graphene? In this paper, based on pentacene, a series of graphene (multi)lithium salts Lin@pentacene (n = 1, 2, 3, 4, 5, and 6) have been designed to answer this question. βtot obviously increases stepwise with an increase in the number of lithium atoms: 1369−1843 for Li@pentacence 2@pentacence 3@pentacence 4@pentacence 5@pentacence, which are much larger than pentacence. This pattern suggests that the lithium salt effect on the first hyperpolarizability is very large. Unexpectedly, when an additional lithium atom is doped into the graphene multilithium salt Li5@pentacence, which leads to Li6@pentacence, the βtot value dramatically increases to a value of 4 501 764 au with a remarkable increase of 302-fold in contrast to Li5@pentacence. On the other hand, when the number of lithium atoms is equal, the location of lithium atoms also affects the βtot value: the closer the lithium atoms are clustered, the larger the βtot value: for Li3@pentacence, 6933 au of system 10 E) are also obtained. The results show that ΔE decreases stepwise with an increase in the number of the lithium atoms, and ΔE of Li6@pentacence sharply decreases to 0.299 eV, which may explain the huge βtot value. This study may stimulate the search for new types of graphene NLO materials based on alkali metals for NLO application

Tuning the First Hyperpolarizabilities of Boron Nitride Nanotubes

Various carbon-substituted boron nitride (8,0) and (4,4) nanotubes are designed for application as nonlinear optical materials. The structure and first (static and frequency-dependent) hyperpolarizabilities of these boron nitride nanotubes are predicted. The substitution of carbon in the boron nitride nanotube clip significantly enhances the first hyperpolarizabilities by up to several orders of magnitude. The doping pattern of the carbon circle and π electron conjugation are crucial in determining the large first hyperpolarizabilities of these nanotubes

Polyoxometalate tri-supported transition metal complexes containing mixed-valent transition metal ions

<div><p>Three compounds, [AsMo₈V₆O₄₂][Cu(2,2’-bpy)₂]₂[Cu(2,2’-bpy)]·4H₂O (<b>1</b>), [PMo₈V₆O₄₂][Cu(2,2’-bpy)₂]₂[Cu(2,2’-bpy)]·3H₂O (<b>2</b>) and [PMo₈V₆O₄₂][Cu(2,2’-bpy)₂]₂[Cu(2,2’-bpy)]·3.5H₂O (<b>3</b>), have been synthesized under hydrothermal conditions and characterized by IR, UV-Vis, XRD, TG, elemental analysis and X-ray diffraction analysis. Single-crystal X-ray structure analysis reveals that <b>1</b> and <b>2</b> are isostructural and isomorphous, whereas <b>2</b> and <b>3</b> are polymorphs. Polymorphs of <b>1</b> have not been synthesized yet. The mixed-valent transition metal ion in <b>1</b>-<b>3</b> have been further confirmed by TG analyses. Catalytic properties of <b>1</b> and <b>2</b> have also been studied.</p></div

pH-controlled assembly of two new supramolecular hybrid compounds based on Keggin polyoxotungstates

<div><p>Two supramolecular compounds based on Keggin polyoxotungstates, (4,4′-H₂bpy){[Cu(4,4′-bpy)]₂[SiW₁₂O₄₀]} (<b>1</b>) and (4,4′-H₂bpy)₂[SiW₁₂O₄₀]·2H₂O (<b>2</b>) have been synthesized and characterized by elemental analyses, IR, UV, XPS spectra, TG analyses, and single crystal X-ray diffraction analyses. Compound <b>1</b> exhibits an infinite 1-D ladder like structure, which is further interconnected into a 3-D supramolecular framework <i>via</i> hydrogen bonding interactions. Compound <b>2</b> contains 4,4′-bipyridine (4,4′-bpy), pseudo-Keggin polyoxoanions [SiW₁₂O₄₀]⁴⁻, and water molecules. Polyoxoanions together with water molecules in <b>2</b> construct a 3-D inorganic supramolecular network through O···O and O···Ow(1) interactions. The electrochemical behaviors and photocatalytic properties of <b>1</b> and <b>2</b> have been investigated.</p></div

Two new halide-containing polyoxometalate-based compounds

<div><p>Two new compounds, [CuCl(Phen)(H₂O)][PW₁₂O₄₀][4,4′-H₂bpy]·1.5H₂O (<b>1</b>) and [Cd₂(Phen)₄Cl₂][HPMo₁₂O₄₀](4,4′-bpy) (<b>2</b>) (bpy = bipyridine, Phen = phenanthroline), have been hydrothermally prepared and characterized by IR, UV–vis, XPS, XRD, elemental analysis, cyclic voltammetry analysis, and single-crystal X-ray diffraction analysis. Compound <b>1</b> exhibits a 1-D chain structure constructed from polyoxometalates (POMs) and transition metal complexes, whereas <b>2</b> presents a supramolecular structure constructed from POMs, metal halide clusters, and organic ligands.</p></div