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14 protocols using chn 2400

1

Purification and Characterization Methods

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All solvents (THF and DMF) were purified before use and kept dry over molecular sieves. All other reagents were of reagent grade and used as received. 1H-NMR, 13C-NMR: Bruker AV-300 spectrometer (Departamento de Química Orgánica, QO). MS: VG Autospec in EI, FAB and FAB-HRMS modes (L-SIMS+), ABSciex QSTAR (ESI+, HRMS), Bruker ULTRAFLEX III (MALDI-TOF/TOF) (HRMS), spectrometers (Servicio Interdepartamental de Investigación, SIdI). Elemental analyses: Perkin-Elmer CHN 2400 automatic analyzers (SIdI).
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2

Characterization of Synthetic Organometallic Complexes

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All synthesized complexes, both intermediate and target compounds, have been characterized by elemental analysis, (Perkin-Elmer CHN 2400), infrared spectroscopy (samples of the complexes were prepared as KBr disks and the spectra were measured in a Bruker model IFS 66 spectrophotometer, 4000 cm-1–400 cm-1), and by 1H NMR, 19F NMR, and 31P NMR (all NMR spectra of all complexes were obtained in CDCl3 solutions via a Varian Unity Plus 400 MHz, tuning the probe to each of the nuclei studied). The novel intermediate complexes were further characterized by MALDI-TOF mass spectroscopy taken on an Autoflex 3 Smart Beam Vertical spectrometer by Brucker Daltonics, with α-cyano-4-hydroxycinnamic acid as the matrix.
The Supporting Information presents all details of the experimental characterizations, data, spectra and all relevant spectral attributions for all complexes synthesized in this article.
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3

Humic Substances Elemental and Spectral Analysis

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The isolation of HAs from soil samples was carried out by alkaline extraction according to the procedure recommended by the International Humic Substances Society [22 ]. Elemental composition of HAs was measured by using CHN 2400 analyzer (Perkin Elmer). Percent oxygen composition was calculated from the equation %O = 100%-(%H+%C+%N) and H/C, O/H, O/C, and C/N atomic ratios were calculated as well as degree of internal oxidation by Zdanow’s formula: ω = [(2O+3N)-H]/C [23 ]. The carboxyl groups (COOH) and sum of carboxylic and phenolic groups (COOH+OH) were investigated according to Dragunowa and Kucharenko [24 ]. The phenol OH groups were evaluated as the difference between the total acidity and carboxyl groups. The E4/E6 and E2/E6 parameters were calculated as the ratio of absorbance measured respectively at 465 and 665 nm as well as 280 and 665 nm of HAs (40 mg dm-3) in a solution of 0.05M NaHCO3 using a UV-VIS spectrometer (Jasco V-520) [25 ]. The Kumada parameter (ΔlogK) was calculated as the difference between the decimal logarithm of absorbance at 400 and 600 nm: ΔlogK = logA400-logA600. Three replicates were performed for each treatment and the results were averaged.
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4

Characterization of Zn(II) Porphyrin Derivatives

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1H NMR spectra were
recorded on a Bruker Advance DRX-400 in pure CDCl3. Due
to the higher solubilities of A4 β-substituted ZnII porphyrins in comparison to those of the trans-A2BC analogues, neither the addition of pyridine-d5 to CDCl3 nor the use of expensive
THF-d8 was necessary to acquire well-resolved
spectra in the 10–2–10–3 M concentration range. Mass spectra were obtained with a Bruker-Daltonics
ICR-FTMS APEX II with an electrospray ionization source or on a VG
Autospec M246 magnetic mass spectrometer with a LSIMS ionic source.
Elemental analyses were carried out with a PerkinElmer CHN 2400 instrument
in the Analytical Laboratories of the Department of Chemistry at the
University of Milan. Electronic absorption spectra were recorded in
CH2Cl2 solution (concentration range of 10–6–10–5 M) at room temperature
on a Shimadzu UV 3600 spectrophotometer. Details on the synthesis
of BP15, BAP1, and
their precursors, including mass spectrometry data, elemental analyses,
and 1H NMR data and spectra, are reported in Figures S1–S6.
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5

Spectroscopic Analysis of Organic Compounds

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All chemicals were purchased from Sigma-Aldrich (Taufkirchen, Germany), and all solvents were purchased from El-Nasr Pharmaceutical Chemicals Company (analytical reagent grade, Egypt). All chemicals were used as supplied without further purification. The melting points were measured by a digital Electrothermal IA 9100 Series apparatus Cole-Parmer, Beacon Road, Stone, Staffordshire, ST15 OSA, UK) and were uncorrected. The spectral analysis was performed at KAUST and Mansura Univesity laboratories C, H, and N analyses on a PerkinElmer CHN 2400. In addition, 1H and 13C NMR spectra were recorded at KAUST on a Bruker 800 MHz NMR Spectrometer using tetramethylsilane (TMS) as the internal standard, chemical shifts were expressed in δ (ppm), and DMSO-d6 was used as the solvent.
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6

Novel Organic Compound Synthesis

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The chemicals and reagents for this study were of analytical reagents and supplied by Sigma Aldrich. Solvents used were purified by the known standard methods. Thin layer chromatography (TLC) experiments were carried out on precoated silica gel plates purchased from Merck Kiesel gel 60F 254, BDH. Digital Stuart SMP3 electric melting point equipment was used to measure the melting points of the compounds. The microwave irradiation reactions (10 mL borosilicate glass vials) were performed using Anton Paar (monowave 300) microwave reactor. Mass spectrometry (EI, 70 eV) measurements were performed on a GC-2010 Shimadzu GCM spectrometer. Perkin-Elmer 293 spectrophotometer instrument was used for the IR measurements (KBr pellets, cm−1). 1H- and 13C-NMR measurements had been performed on a Varian Mercury 300 MHz spectrometer. Deuterated DMSO solutions of the samples with TMS as internal standard were used for the analysis. The microanalytical (CHN) analyses were carried out using a Perkin-Elmer analyzer (CHN-2400). Accuracy of the data were within ± 0.3% of calculated values.
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7

Characterization of Metal-Organic Complexes

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Chemicals, including
Zn(NO3)2·6H2O, Cu(NO3)2·3H2O, H2BDC, and bpy, and
all solvents were commercially purchased and directly used without
further purification.
Elemental analyses (EA) for carbon, hydrogen,
and nitrogen were performed on a PerkinElmer CHN-2400 elemental analyzer.
Infrared spectra (IR) were recorded in the wavenumber ranges of 400–4000
cm–1 on an AVATAR-360 spectrophotometer using KBr
pellets. The UV–vis spectra were recorded using a PerkinElmer
Lambda 950 UV–vis spectrometer. The 1H NMR spectra
were recorded in DMSO-d6 on a Bruker 400
MHz. The photoluminescence (PL) spectra were measured with an Edinburgh
Instruments FLS920P fluorescence spectrometer at room temperature.
The emission decay lifetime and quantum yield were recorded at room
temperature in an Edinburgh FLS980 fluorescence spectrometer. Magnetic
susceptibility was measured for the polycrystalline sample in the
temperature ranges of 2–300 K using a Quantum Design MPMS-5S
superconducting quantum interference device (SQUID) magnetometer,
and the diamagnetism arising from the core of atoms was not removed
from the experimental magnetic susceptibility.
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8

Comprehensive Characterization of Metal Complexes

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Elemental C, H, N analysis was carried out on a PerkinElmer CHN 2400 (Waltham, MA, USA). The percentage of metal ions was determined by using the atomic absorption method with a PYE-UNICAM SP 1900 spectrometer (Cambridge, UK) fit with the corresponding lamp. IR spectra were recorded from KBr discs using an FT/IR-460 Plus model Jasco-32 spectrophotometer (Easton, PA, USA) in the range from 4000 to 400 cm−1. 1H NMR spectra were recorded on a Varian 400 NMR spectrometer (Urbana, IL, USA) using CD3OD as solvent. Electronic spectra were obtained using T80 UV/Vis spectrometer (Taylors, SC, USA) PG Instruments Ltd. Magnetic susceptibilities of the powdered samples were measured on a Sherwood scientific magnetic balance (Cambridge, UK) using the Gouy method with Hg[Co(SCN)4] as calibrant. Molar conductance of 1 × 10−3 M solutions of ligand and metal complexes in DMF was measured at room temperature using a CONSORT K410 (Turnhout, Belgium). All measurements were carried out at ambient temperature with freshly prepared solutions. Melting points were recorded on a Buchi apparatus.
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9

Spectroscopic Characterization of Organic Compounds

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1H NMR (400 MHz) and 13C NMR (100 MHz) spectra were measured in CDCl3 or DMSO-d6 on a Varian Mercury Plus spectrometer. Chemical shifts (δ) are reported in ppm downfield from TMS as internal standard, and coupling constants (J) are given in hertz (Hz). Melting points were determined on a Kofler micro melting point apparatus and are uncorrected. Infrared spectra were recorded on an Avatar FT-IR 6700 (Thermo Scientific, UK) using an attenuated total reflectance (ATR) method in the range 4000–400 cm−1. Microanalyses were performed with a Perkin-Elmer, CHN 2400 elemental analyzer. The progress of chemical reactions was monitored on TLC-sheets ALUGRAM® SIL G/UV254 (Macherey-Nagel, Dueren, Germany). Detection was carried out with ultraviolet light (254 nm). Column chromatography was performed on silica gel, Kieselgel 60 Merck Type 9385 (0.040–0.063). All commercial reagents were used in the highest available purity without further purification.
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10

Analytical Techniques for Material Characterization

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The following is a list of the different types of analysis and their respective models:
Type of AnalysisModelsSEMQuanta FEG 250 equipmentTEMJEOL 100s microscopyMagnetic momentMagnetic Susceptibility BalanceElectronic spectraUV2 Unicam UV/Vis SpectrophotometerFTIR spectraBruker FTIR SpectrophotometerConductanceJenway 4010 conductivity meterElemental analyses (C,H,N)Perkin Elmer CHN 2400Metal ions (Mn, Co, Cu, Ni)An atomic absorption spectrometer model PYE-UNICAM SP 1900
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