91224 - MATERIALS ORGANIC CHEMISTRY WITH LABORATORY

Conoscenze e abilità da conseguire

At the end of the course the student has acquired knowledges towards the design and synthesis of conjugated organic compounds and laboratory experience of multi-step synthesis and analytical/spectroscopic characterization of conjugated organic molecular materials.

Contenuti

The student that plans to attend the course, in order to get maximum comprehension of the topics of the lessons must be confident with the programmes of the basic organic chemistry with particular concern to the synthesis and functionalization of the main organic functional groups (from alkanes to carboxylic derivate). The text book “Organic Chemistry” by J. Clayden, N. Greeves, S. Warren is kindly suggested. Moreover, the student should already be practice with common lab glass-ware, with the setting of an organic reaction, monitoring of the process by means of TLC and classic work-up. Finally, the student is supposed to known how to get structural information on a title organic species via NMR-spectroscopy 1H and 13C.

1. Organic materials for opto-electronic
1.1. Basis of main p-conjugated polymeric
1.2. The electroluminescence
1.3. Structure/propriety relationships of the conjugated organic compounds;
1.3.1. Steric effects
1.3.2 Electronic effects
1.4 Organic compounds with blue-emission
1.4.1 Poly-fluorene

2. Synthesis and functionalization of heteroaromatic compounds
2.1. Pyridine: resonance formula and dipole moment
2.2. Quinoline: resonance formula and dipole moment
2.3. Azoles: resonance formula and dipole moment
2.4. Pyrrole: resonance formula and dipole moment and electronic analogy with Cp anion.
2.5 Furan and thiophene: resonance formula and dipole moment
2.6 Main electron-rinc heteroaromatic benzo-fused: resonance formula and dipole moment
2.7 Reactivity of pyridine towards electrophilic reactions
2.8 Electrophilic substitution of quinoline to the C atom
2.9 Regiochemistry of the SEAr in biaryl compounds
2.10 Acidity of the NH groups in azoles and analogoues
2.11 Lithiation of aromatic 5 and 6-membered rings. Activation of the C-H
2.12 Lithiation of aromatic 5 and 6-membered rings: halogen exchange
2.13 Radical halogenation (NBS) of electron-rich aromatic compounds
2.14 Synthesis of aryl-boronic, aryl-sylane and aryl stannane compounds

3. Pd-catalyzed cross-coupling reactions
3.1 The Suzuki-Miyaura reactions
3.1.1 Scope, limitations and mechanistic details
3.2 The Hiyama reaction
3.2.1 Scope, limitations and mechanistic details
3.3 The Stille reaction
3.3.1 Scope, limitations and mechanistic details
3.4 The Mirozoki-Heck reaction
3.4.1 Scope, limitations and mechanistic details
3.5 The Hiyama reaction
3.5.1 Scope, limitations and mechanistic details
3.6 The Buchwald-Hartwig reaction
3.6.1 Scope, limitations and mechanistic details
3.7 The Cassar-Sonogashira reactop
3.7.1 Scope, limitations and mechanistic details

4. The metathesis reaction
4.1 The metathesis ene-ene
4.1.1 Metallo-carbenes: synthesis and properties
4.1.2 The Chauvin' postulate
4.1.3 The Grubb's catalysts (I and II generation) and the Grubbs-Hoveyda catalysts
4.1.4 Types of metathesis reactions
4.1.5 Dissociative mechanism: the ring-closing case
4.1.6 The cross-metathesis reaction
4.1.7 Thermodynamic aspects in the RCM
4.1.8 Application of the RCM to the synthesis of polyfunctionalized compounds
4.2 The metathesis ene-yno
4.2.1 The reaction machinery
4.2.2 Application of the ene-yno to the synthesis of polyfunctionalized compounds
4.3 The metathesis yne-yno
4.3.1 Reaction machinery
4.3.2 Application of the ene-yno to the synthesis of stereochemically defined unsaturated macrocycles
4.3.3 Application of the ene-yno to the synthesis of functionalized poly-acenes

5. The click chemistry
5.1 Definition and early achievements
5.2 Synhesis of organo-azides
5.3 CuAAc: reaction mechanism
5.4 CuAAC: synthetic applications

6. Laboratory work

6.1 Review of the main techniques in the organic chemistry laboratory (e.g. working under inert atmosphere, TLC, flash chromatography)
6.2 Review of structure determination by NMR and mass spectroscopy.
6.3 Sequential multi-step synthesis and characterization of an organic dyes with emission properties.
6.4 Sequential multi-step synthesis and characterization of a luminescent iridium complex.

Testi/Bibliografia

Handbook of MetathesisEditor(s):

• Robert H. Grubbs
• Anna G. Wenzel
• Daniel J. O'Leary
• Ezat Khosravi

Metodi didattici

Theoretical lessons 24 hs (use of black-board, and projection of slides via ppt presentations).

Attendance: The course is characterized by a compulsory attendance to the practical experiences.

 

As concerns the teaching methods of this course unit, all students must attend Module 1, 2 [https://www.unibo.it/en/services-and-opportunities/health-and-assistance/health-and-safety/online-course-on-health-and-safety-in-study-and-internship-areas] online, while Module 3 on health and safety is to be attended in class or on Microsoft Teams according to the modality chosen by the teacher. Information about Module 3 attendance schedule is available on the website of your degree programme.

Modalità di verifica e valutazione dell'apprendimento

The overall grade of the exam will be expressed in 30th and it will derive from the assessment of: 1) the oral exam regarding the theorethical part (Modulo 1, max: 30/30), 2) the presentation related to the laboratory and personal assessment of the candidate during the working time in the laboratory classes (Modulo 2, max 30/30). The final mark will be generated by the weighted average of the two marks with the theorethical part contribuiting for 2/3 and the laboratory part contribuiting for 1/3 of the total mark.

• An overall grade of "not sufficient" (score < 18/30) indicates significant gaps in course content, failure to answer questions, or inadequate responses. The scores from the laboratory practice and the final presentation are never insufficient by themselves.
• An overall grade of "sufficient to fair" (18–24/30) indicates an acceptable level of preparation, but with noticeable gaps in knowledge or inadequately studied topics.

• An overall grade of "good" (25–28/30) indicates that the student has a solid understanding of the course content and is able to make connections between different parts of the program. The student also successfully addressed the laboratory component and present a well-constructed report.

• An overall grade of "excellent" (29–30/30 cum laude) indicates a thorough and in-depth preparation across the entire course program, with a clear and coherent understanding. The laboratory presentation is also of high quality and demonstrates extensive knowledge of the experimental techniques discussed during the practical sessions.

The student will be allowed to face the examination only if in possession of documented attendance of the practical lessons (75% of the total).

 

Students with learning disorders and\or temporary or permanent disabilities: please, contact the office responsible (https://site.unibo.it/studenti-con-disabilita-e-dsa/en/for-students ) as soon as possible so that they can propose acceptable adjustments. The request for adaptation must be submitted in advance (15 days before the exam date) to the lecturer, who will assess the appropriateness of the adjustments, taking into account the teaching objectives.

Strumenti a supporto della didattica

The didactic material will be provided by the Professor to the students in electronic format. Moreover, all the literature articles describing the exercises discussed during the class-room will be available. All in one, the students will be asked to prepare the examination by studying notes taken during the classes.

Orario di ricevimento

Consulta il sito web di Marco Bandini

Consulta il sito web di Andrea Gualandi